Polymer-analogous Transformations Research Articles

New Antibacterial and Antioxidant Chitin Derivatives: Ultrasonic Preparation and Biological Effects.

This work focuses on the first use of ultrasonic phenol-ene coupling as a polymer analogous transformation. The ultrasonic reaction was introduced into chitin chemistry, resulting in the fast and convenient preparation of new water-soluble cationic chitin derivatives. Since water-soluble derivatives of fully deacetylated chitin are poorly described in the literature, the synthesis of each new type of these derivatives is a significant event in polysaccharide chemistry. Polycations, or cationic polymers, are of particular interest as antibacterial agents. Consequently, the resulting polymers were tested for their antibacterial activity and toxicity. We found that the highly substituted polymer of medium molecular weight exhibited the most pronounced in vitro antibacterial effect. We prepared nanoparticles using the ionic gelation technique. The most effective in vitro antibacterial chitin-based systems were tested in vivo in rats. These tests demonstrated outstanding antibacterial effects combined with an absence of toxicity. Additionally, we found that the resulting polymers, unlike their nanoparticle counterparts, also exhibited strong antioxidant effects. In summary, we demonstrated the effectiveness of ultrasound in polymer chemistry and highlighted the importance of the sonochemical approach in the chemical modification of polysaccharides. This approach enables the synthesis of derivatives with improved physicochemical and biological properties.

Polymeric carriers of vanadyl ions based on copolymers of N-vinylpyrrolidone with vinylimines

In this study, a series of new chelating copolymers containing 20% azomethine groups, poly(N-vinylpyrrolidone-co-vinylsalicylideneimine) (poly[VP-co-VSalI]), poly(N-vinylpyrrolidone-co-vinylpicolinideneimine) (poly[VP-co-VPicI]), poly(N-vinylpyrrolidone-co-vinylpyridoxylideneimine) (poly[VP-co-VPyrI]) with M = 63000 Da and their vanadium(IV) complexes – poly(VP-co-VSalI)-VO, poly(VP-co-VPicI)-VO, poly(VP-co-VPyrI)-VO, were designed and synthesized. These are intended for the delivery and pH-dependent release of vanadium species in the intestine environment. The chelating polymers were obtained from poly(N-vinylpyrrolidone-co-N-vinylamine) (poly[VP-VAm]) by polymer-analogous transformations with the corresponding aldehydes. The vanadium content, determined by ICP-AES and spectrophotometric methods, was 5.36%, 4.99%, and 9.1% of the dry mass for poly(VP-co-VSalI)-VO, poly(VP-co-VPyrI)-VO, and poly(VP-co-VPicI)-VO, respectively. XPS data confirmed that only vanadium(IV) is presented in the complexes. All complexes demonstrated a pH-dependent release of low molecular weight vanadium species, making them promising candidates for the development of vanadium-containing systems for oral administration. These systems protect the main vanadium content in the stomach but can release biologically active ions in the intestine.

Synthesis and modification of copolymers of stearyl methacrylate and maleic anhydride and study of their effect on low-temperature characteristics of diesel fuel

Polymer-analogous transformations have been used to modify copolymers of stearyl methacrylate with maleic anhydride synthesized under radical polymerization conditions using reversible chain transfer agents of various structures. It has been established that copolymer of stearyl methacrylate with maleic anhydride modified by 25% with octanol-1 has a high depressant effect for a pour point of minus 19°С and at the same time significantly reduces both the cloud point values and the maximum filterability temperature of diesel fuel. In this regard, the obtained modified copolymers may be of interest in terms of their practical use as fuel additives.

Structural and Morphological Features of Anisotropic Chitosan Hydrogels Obtained by Ion-Induced Neutralization in a Triethanolamine Medium.

For the first time, anisotropic hydrogel material with a highly oriented structure was obtained by the chemical reaction of polymer-analogous transformation of chitosan glycolate-chitosan base using triethanolamine (TEA) as a neutralizing reagent. Tangential bands or concentric rings, depending on the reaction conditions, represent the structural anisotropy of the hydrogel. The formation kinetics and the ratio of the positions of these periodic structures are described by the Liesegang regularities. Detailed information about the bands is given (formation time, coordinate, width, height, and formation rate). The supramolecular ordering anisotropy of the resulting material was evaluated both by the number of Liesegang bands (up to 16) and by the average values of the TEA diffusion coefficient ((15-153) × 10-10 and (4-33) × 10-10 m2/s), corresponding to the initial and final phase of the experiment, respectively. The minimum chitosan concentration required to form a spatial gel network and, accordingly, a layered anisotropic structure was estimated as 1.5 g/dL. Morphological features of the structural anisotropic ordering of chitosan Liesegang structures are visualized by scanning electron microscopy. The hemocompatibility of the material obtained was tested, and its high sorption-desorption properties were evaluated using the example of loading-release of cholecalciferol (loading degree ~35-45%, 100% desorption within 25-28 h), which was observed for a hydrophobic substance inside a chitosan-based material for the first time.

Polymer-analogous transformations of poly(N-vinylpyrrolidone) to produce new complexing macromolecular systems

A new polymer-analogous transformations of poly(N-vinylpyrrolidone) was used to prepare new complex-forming macromolecular systems containing thiourea and thio-semicarbazone sites. Two variants of modification were realized, namely, the method including the preliminary in situ activation of nucleophilic centres of the polymer amide fragments with dimethyl sulfate followed by introducing nucleophilic agents into the system, and the method including partial hydrolysis of poly(N-vinylpyrrolidone) followed by the amide coupling. The obtained modified polymeric materials react with silver ions in aqueous solution.

One-Step Synthesis of Functional Sulfonated Polynaphthoylenebenzimidazoles for Biosensing Applications

Polynaphthoylenebenzimidazoles containing functional sulfo groups were synthesized by a one-step method in a sulfuric acid medium with oleum. A polymer-analogous transformation of these polymers with aqueous solutions of metal salts (K, Ca, and Cr) was carried out. Their chemical structure was characterized by FTIR, NMR, and elemental analysis. Polymer salt coatings were deposited on QCM sensor surfaces by electron beam-induced vacuum deposition. The morphology of the coatings was characterized by AFM. It was shown that the coatings formed from a series of polymer salts have different adsorption activity in acetaminophen–water solution compared to distilled water. The QCM results indicate that sensor signal correlates with polymer coating thickness, morphology, and its chemical composition.

Multifunctional modifier for regulating the properties of concrete mixtures

The purpose of this work is the synthesis of new highmolecular surfactants polyalkylacrylates and the establishment of correlations between their colloidal chemical properties. Well-known methods for the synthesis and determination of the properties of surfactants were used. New high molecular surface-active substances (HMSAS) were obtained based on the reaction of polymer-analogous transformations. The resulting copolymers contain side hydrocarbon radicals of various lengths. Polyalkylacrylates were obtained by esterification with aliphatic alcohols (butyl, octyl, decyl) in a mixture of organic solvents and the presence of a catalyst, sulfuric acid. The surface activity and foaming ability of the obtained new HMSAS in aqueous solutions have been studied. The results obtained showed that with an increase in the length of the aliphatic hydrocarbon radical in the chain of macromolecules, the surface activity of polyalkylacrylates increases. An analysis of the results showed a good correlation between foaming and surface activity of the investigated HMSAS. Based on research, it was found that the stability of the foams is largely determined by the interaction of the HMSAS molecules in the monolayer.

A GAP Replacement, Part 2: Preparation of Poly(3-azidooxetane) via Azidation of Poly(3-tosyloxyoxetane) and Poly(3-mesyloxyoxetane).

Despite the variety of energetic polyoxetane binders, the oxirane-based glycidyl azide polymer (GAP) has largely succeeded in the market due to its advantageous properties. Nevertheless, it suffers from various drawbacks such as non-uniform chain termination, possible chlorine content (flame retardant), and toxic epichlorohydrin required for its synthesis. These problems can be bypassed using the structurally related poly(3-azidooxetane). Unfortunately, it is only accessible in moderate yield by polymerization of 3-azidooxetane. Herein, we describe its synthesis by polymer-analogous transformation using the new polymers poly(3-tosyloxyoxetane) and poly(3-mesyloxyoxetane) as precursors. This results in a significantly increased yield and improved safety as handling of the very sensitive 3-azidooxetane is avoided. The aforementioned prepolymers were prepared using boron trifluoride etherate as well as triisobutylaluminum as catalysts. The latter provides polymers of particularly high molecular weight, and the corresponding poly(3-azidooxetane) species was obtained and studied for the first time. In order to shed light on the applicability of poly(3-azidooxetane) as a GAP substitute, it was thoroughly studied with regard to thermal behavior, energetic performance (EXPLO5), plasticizer compatibility, and curing. Moreover, the aquatic toxicity of all involved monomers was analyzed and compared to epichlorohydrin. Here, poly(3-azidooxetane) turned out as a fully adequate, if not more environmentally benign, substitute.

Molecular Brushes with a Polyimide Backbone and Poly(ε-Caprolactone) Side Chains by the Combination of ATRP, ROP, and CuAAC.

An approach to the synthesis of the novel molecular brushes with a polyimide (PI) backbone and poly(ε-caprolactone) (PCL) side chains was developed. To obtain such copolymers, a combination of various synthesis methods was used, including polycondensation, atom transfer radical polymerization (ATRP), ring opening polymerization (ROP), and Cu (I)-catalyzed azide-alkyne Huisgen cycloaddition (CuAAC). ATRP of 2-hydroxyethyl methacrylate (HEMA) on PI macroinitiator followed by ROP of ε-caprolactone (CL) provided a “brush on brush” structure PI-g-(PHEMA-g-PCL). For the synthesis of PI-g-PCL two synthetic routes combining ROP and CuAAC were compared: (1) polymer-analogous transformations of a multicenter PI macroinitiator with an initiating hydroxyl group separated from the main chain by a triazole ring followed by ROP of CL, or (2) a separate synthesis of macromonomers with the desirable functional groups (polyimide with azide groups and PCL with terminal alkyne groups), followed by a click reaction. Results showed that the first approach allows to obtain graft copolymers with a PI backbone and relatively short PCL side chains. While the implementation of the second approach leads to a more significant increase in the molecular weight, but unreacted linear PCL remains in the system. Obtained macroinitiators and copolymers were characterized using 1H NMR and IR spectroscopy, their molecular weight characteristics were determined by SEC with triple detection. TGA and DSC were used to determine their thermal properties. X-ray scattering data showed that the introduction of a polyimide block into the polycaprolactone matrix did not change the degree of crystallinity of PCL.

Metal Derivatives of Sulfonated Polyphenylquinoxaline

The polymer-analogous transformations of an aromatic ionogenic polymer, namely, sulfonated polyphenylquinoxaline afford a range of polymer salts bearing alkali (Li+, Na+, K+), alkaline earth (Mg2+, Са2+, Ba 2+), and transition di- (Cu2+, Ni2+, Zn2+) and trivalent (La3+, In3+) metal ions. The resulting polymers are characterized by elemental and thermogravimetric analyses. The solubility and rheological properties of their dilute and concentrated solutions as well as sensor properties of the coatings based on these polymer salts are explored.

New polycarbonate siloxanes based on siloxane-<i>N</i>-phthalimidines

Objectives. Polymeric carbonate siloxanes containing a siloxane-N-phthalimidine group in the chain frame are new synthetic comb-like macromolecule systems. This work aims to study the possibility of applying them in the form of film materials for heat-resistant, high-performance gas-permeable membranes.Methods. Comb-like polycarbonate siloxanes of the siloxane-containing polyether class were obtained using various polycondensation methods. i.e., by the polymer-analogous transformation of polycarbonate-allyl-N-phthalimidines, using their reaction in an alkyl hydride siloxane solution; polycondensation of N-(3-(pentamethyldisiloxane)-propyl)-3,3-bis-(4'-hydroxyphenyl)phthalimidine with diphenylolpropane bis-chloroformate in a solution using triethylamine as an acceptor of hydrochloric acid; interphase polycondensation of the above reagents in a dichloromethane aqueous alkali system. The structures of the obtained initial and polymeric compounds were confirmed by proton nuclear magnetic resonance spectroscopy and elemental analysis. All of the synthesized comb-like copolymers had good solubility in several available solvents and film formations.Results. The new comb-like polycarbonate siloxanes had high thermal stability. According to thermogravimetric analysis, the introduction of up to 20 wt % siloxane units makes it possible to increase the heat resistance of polycarbonate siloxanes by 25 °C. Concurrently, their glasstransition temperature reaches 160 °C. Copolymers of polycarbonate siloxanes in the form of films have a high tensile strength above 50 MPa and an elastic modulus of up to 2000 MPa. The permeability coefficients of gases through a copolymer of polycarbonate siloxanes in the form of a film for several gases surpass the permeability of industrial polycarbonate from diphenylolpropane and fluorine-containing siloxane polycarbonate.Conclusions. The results achieved indicate the possibility of creating new polymeric combshaped siloxane systems with a variable structure that can contribute to obtaining the properties desired from them. Combined with high selectivity gas separation, this makes it possible to use such comb-shaped polycarbonate siloxanes as film membrane materials with an increased operating temperature range.

Allyl group-containing polyvinylphosphonates as a flexible platform for the selective introduction of functional groups via polymer-analogous transformations.

Polyvinylphosphonates are highly promising candidates for (bio)medical applications as they exhibit a tunable lower critical solution temperature, high biocompatibility of homo- and copolymers, and a broad foundation for post-synthetic modifications. In this work we explored polymer-analogous transformations with statistical polyvinylphosphonates comprising diethyl vinylphosphonate (DEVP) and diallyl vinylphosphonate (DAlVP). The C Created by potrace 1.16, written by Peter Selinger 2001-2019 ]]> C double bonds were used as a starting point for a cascade of organic transformations. Initially, the reactive moieties were successfully introduced via bromination, epoxidations with OXONE and mCPBA, or thiol–ene click chemistry with methyl thioglycolate (6). The obtained substrates were then employed in a variety of consecutive reactions depending on the introduced functional motif: (1) the brominated substrates were converted with sodium azide to enable the copper-mediated alkyne–azide coupling with phenylacetylene (1). (2) The epoxides were reacted with sodium azide for an alkyne–azide click coupling with 1 as well as small nucleophilic compounds (phenol (2), benzylamine (3), and 4-amino-2,1,3-benzothiadiazol (4)). Afterwards the non-converted allyl groups were reacted with thiochloesterol (5) to form complex polymer conjugates. (3) An acid-labile hydrazone-linked conjugate was formed in a two-step approach. The polymeric substrates were characterized by NMR, FTIR, and UV/Vis spectroscopy as well as elemental analysis and gel permeation chromatography to monitor the structural changes of the polymeric substrates and to prove the success of these modification approaches.

Effect of the Degree of Sulfoethylation of Polyaminostyrene on Its Acid-Basic Properties and Specificity of Interaction with Transition Metal Ions

A method was developed for the preparation of N-2-sulfoethylated polyaminostyrene (SEPAS) by gel synthesis with a degree of substitution up to 1.2. The composition and structure of the products of polymer-analogous transformations were characterized using elemental analysis and FT-IR spectroscopy. It was found that an increase in the degree of sulfoethylation decreases the basicity of amino groups. This leads to an increase in the selectivity coefficient KAg(I)/Cu(II) in an ammonium acetate buffer solution in the pH range 5.5–6.0, which makes it possible to use SEPAS for the selective extraction of silver(I) from solutions of complex composition. The degree of sulfoethylation does not affect the rate at which the sorption equilibrium is established.

SYNTHESIS OF TRITERPENE POLYMER CONSTRUCTIONS

The pentacyclic triterpenoids betulin and betulonic acid are promising sources of new biologically active compounds. Grafting them onto polymer matrices leads to the formation of effective dosage forms compared to the original drug. On the basis of betulin and betulonic acid, the synthesis of polymer structures with a fragment of triterpene in the side chain was carried out. New triterpene-containing polymer ensembles were obtained by the method of polymer-analogous transformations of copolymers of N-vinylpyrrolidone with N-(n-carboxy) phenylmaleimide and p-aminostyrene. By crosslinking the carboxyl groups of the copolymer of N-vinylpyrrolidone with N-(n-carboxy) phenylmaleimide with betulin hydroxyl groups and the reaction of the amino groups of the copolymer of N-vinyl pyrrolidone with p-aminopyrol with carboxyl groups of betulonic acid, polymer structures with polycyclic triterpene fragments are obtained. The resulting polymer ensembles have higher activity against melanoma compared to the original copolymers. A polymer based on a copolymer of N-vinylpyrrolidone with N-(n-carboxy) phenylmaleimide and betulin at a concentration of 40.48 μM inhibits 50% of MS cells, while 50% of MS cells die under the influence of 68.29 μM betulin. New triterpene-containing polymer ensembles are promising for the development of new biologically active polymer bioconjugates.

Ultrasound-assisted catalyst-free thiol-yne click reaction in chitosan chemistry: Antibacterial and transfection activity of novel cationic chitosan derivatives and their based nanoparticles

In this work, we demonstrate that the thiol-yne click reaction could be efficiently mediated by ultrasonic irradiation and implement the ultrasound-assisted thiol-yne click reaction to chitosan chemistry as a polymer-analogous transformation. We optimize power and frequency of ultrasound to preserve selectivity of the click reaction and avoid ultrasonic degradation of the chitosan polymer chain. Thus, we obtain a new water-soluble betaine. Using ionic gelation of the obtained betaine derivatives of chitosan, we prepare nanoparticles with a unimodal size distribution. Furthermore, we present results of antibacterial and transfection activity tests for the chitosan derivatives and their based nanoparticles. The derivative with a medium molecular weight and a high degree of substitution demonstrated the best antibacterial effect. It derived nanoparticles with a size of ca. 100 nm and ζ-potential of ca. +69 mV revealed even higher antibacterial activity, slightly superior to commercial antibiotics ampicillin and gentamicin. On the contrary, the obtained polymers possess a much more pronounced transfection activity as compared with their based nanoparticles and species with a low degree of substitution acts as the most efficient transfecting agent. Moreover, the obtained betaine chitosan derivatives as well as their derived nanoparticles are non-toxic.

Obtaining and prospects for the use of hydrazide N-vinylsuccinamic acid copolymers as a carrier of biofunctional substances with directional effect

Water-soluble (co) polymers of N-vinylsuccinamic acid hydrazide are obtained as a result of polymer-analogous transformations in the interaction of hydrazine-hydrate of vinyl acetate copolymers with vinyl succinimide and polyvinyl succinimide. Using IR spectroscopy, potentiometric titration, elemental analysis, their structure and composition were established. The possibility of using copolymers as carriers of biofunctional substances of an acidic nature is shown.

Synthesis and investigation of properties of new chelate sorbent for water purification

Polymer analogous transformations of a “nitron” fiber were established and a new amino carboxylic fibrous cation exchanger FIBAN X-2 was obtained. It is shown that FIBAN X-2 is an effective sorbent of heavy and non-ferrous metals from multi-ionic aqueous solutions, regardless of the method of fiber amination. The cation exchanger obtained by amination of a “nitron” fiber in the vapor phase absorbs Mn+2 twice as much as the ion exchanger obtained by amination in the aqueous solution.

Ultrasound-assisted Cu(I)-catalyzed azide-alkyne click cycloaddition as polymer-analogous transformation in chitosan chemistry. High antibacterial and transfection activity of novel triazol betaine chitosan derivatives and their nanoparticles

In this work, we involved ultrasound-assisted click CuAAC in chitosan chemistry. Ultrasound-mediated CuAAC between propargylic ester of betaine and azido chitosan derivative proceeds fast in water under aerobic conditions and gives rise novel water-soluble triazole betaine chitosan derivatives. Using ionic gelation technique, we prepared and characterized nanoparticles from the synthesized chitosan derivatives. We studied antibacterial and transfection activity of the novel chitosan derivatives and their nanoparticles. The nanoparticles with size ca. 100 nm and ζ-potential ca. +65 mV proved to possess outstanding antibacterial activity, which is much more than that of the triazole betaine derivatives in their native form, and it is equal to the activity of ampicillin and gentamicin. Opposite, triazole betaine chitosan derivatives in their native form are characterized by remarkable transfection activity as compared with their nanoparticles. The most active triazole betaine chitosan derivatives are derivatives of moderate molecular weight with moderate degree of substitution. Their transfection activity is extremely high for chitosan species and it is comparable (values of the same order) with activity of Lipofectin – commercially available gene delivery vector.

Sulfoethylated polyethylenimine: synthesis in gel and sorption properties

Using the gel synthesis approach of polymer-analogous transformations, N-sulfoethylation of polyethylenimine was carried out by treating the polymer with sodium vinyl sulfonate. The compositions and structures of the products were characterized by elemental analysis, FT-IR spectroscopy, and 1H NMR spectroscopy. At pH 3.0–4.5 sulfoethylated polyethylenimine can selectively extract AgI and CuII from an ammonia—acetate buffer solution in the presence of a series of transition and alkaline-earth metals. At pH > 6.5 the sorbent can be used for the group extraction of a number of transition metal ions. The structural feature of the obtained derivative eliminates the selectivity of sorption of AgI ions compared to CuII ions, which has previously been revealed for the sulfoethylated derivatives of chitosan and polyaminostyrene.

Thiocarbamoylation of Chlorosulfonated Polystyrene for Preparing Sorbents for Noble Metal Ions

A new sorbent for noble metal ions, ensuring selective recovery of Au(III) ions from aqueous solutions containing interfering 3d metal ions, was suggested. The new functional derivative, poly(thiocarbamoylsulfostyre ne), was prepared by treatment of poly(chlorosulfostyrene) with thiourea. At the total degree of functionalization with sulfo and thiourea groups of up to 1.0, the degree of thiocarbamoylation can be controlled in the range from 10 to 75%. The composition and structure of the polymer-analogous transformation products were characterized by elemental analysis, Fourier IR spectroscopy, and thermal gravimetric analysis with IR identification of the decomposition products. Evaluation of the sorption activity of poly(thiocarbamoylsulfostyrene) has shown that the sorbent takes up Au(III) ions virtually quantitatively with high selectivity from an aqueous solution containing Co(II), Fe(III), Pd(II), and Ni(II) ions.