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Interaction of chitosan and its derivatives with proteins of animal blood at blood pH relevant conditions is of a particular interest for construction of antimicrobial chitosan/protein-based drug delivery systems. In this work, the interaction of a series of N-reacetylated oligochitosans (RA-CHI) having M w of 10-12 kDa and differing in the degree of acetylation (DA 19, 24, and 40 %) with bovine serum albumin (BSA) in alkalescent media is described in first. It is shown that RA-CHI forms soluble complexes with BSA in solutions with pH 7.4 and a low ionic strength. Light scattering study shows that soluble RA-CHI complexes have spherical form with the radius of about 100 nm. Circular dichroism, fluorescent spectroscopy, and micro-IR spectroscopy studies show that the secondary structure of BSA in soluble complexes remain intact. Isothermal titration calorimetry of RA-CHI with DA 24 % and BSA mixing in the buffers with different ionization heats reveals a significant contribution of electrostatic forces to the binding process and an additional ionization of chitosan due to the proton transfer from the buffer substance. An increase of ionic strength to the blood relevant value 0.15 M suppresses the binding. It is shown that application of RA-CHI with higher DA value leads to a decrease in the affinity of RA-CHI to BSA and an alteration of the interaction mechanism. The finding opens an opportunity to the application of N-reacetylated chitosan derivatives in the complex systems compatible with blood plasma proteins., Competing Interests: Declaration of competing interest The authors confirm that all elements of the article comply with the journal's publishing ethics policy, each author has made an equal contribution to the article and approved the submission. The authors declare that there is no conflict of interest, and the work described in the manuscript is not submitted to another journal., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Herein, we describe in first the application of squid pens for the preparation of pharmaceutical-grade oligochitosan hydrochloride with the physicochemical characteristics corresponding with the requirements of the European Pharmacopoeia. It is shown that the use of specific properties of squid pens as a source of parent chitosan allows preparing the product with a high yield at relatively moderate process conditions used for squid pens treatments and chitosan depolymerization., Competing Interests: Declaration of competing interest The authors confirm that all elements of the article comply with the journal's publishing ethics policy, each author has made an equal contribution to the article and approved the submission. The authors declare that there is no conflict of interest, and the work described in the manuscript is not submitted to another journal., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The interaction between carboxymethyl cellulose and partially reacetylated chitosan soluble in acidic and alkaline aqueous media is studied by light scattering and isothermal titration calorimetry in a wide pH range. It is shown that the formation of polyelectrolyte complexes (PEC) can occur in the pH range of 6-8, while this pair of polyelectrolytes loses the ability to complexation upon transition to a more alkaline medium. The revealed dependence of the observed enthalpy of interaction on the ionization enthalpy of the buffer indicates the participation of proton transfer from the buffer substance to chitosan and its additional ionization in the binding process. This phenomenon is first observed in a mixture of a weak polybase chitosan and a weak polyacid. The possibility to obtain soluble nonstoichiometric PEC by a direct mixing of the components in a weakly alkaline medium is shown. The resulting PECs are polymolecular particles in shape close to homogeneous spheres with a radius of about 100 nm. The obtained results are promising for creating of biocompatible and biodegradable drug delivery systems., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Inesa V. Blagodatskikh reports financial support was provided by Russian Science Foundation., (Copyright © 2023 Elsevier B.V. All rights reserved.)

In this work, the interaction between the negatively charged surfactant sodium dodecyl sulfate (SDS) and partially N-reacetylated chitosan (RA-CHI), which is soluble at pH range up to pH 12, is studied in a wide pH range including alkaline media by light scattering (LS) and isothermic titration calorimetry (ITC). It is shown that in the weakly alkaline medium (pH 7.4), RA-CHI/SDS interaction is exothermic and cooperative. This interaction is found to be coupled with proton transfer from the buffer substance to chitosan as it is revealed by the dependence of the measured heat release on the ionization enthalpy of the buffer. At higher pH values (pH > 8), another mechanism of interaction is observed that include SDS micellization induced by hydrophobic interactions with polymer segments, so that no phase separation occurred in these mixtures. The results obtained can contribute to expand the knowledge about application of chitosan for preparation of pharmaceutical and cosmetic compositions containing anionic surfactants., (Copyright © 2022. Published by Elsevier B.V.)

Polymer microgels, including those based on interpenetrating networks (IPNs), are currently vastly studied, and their practical applications are a matter of thriving research. In this work, we show the perspective for the use of polyelectrolyte IPN microgels either as scavengers or carriers of antiseptic substances. Here, we report that poly- N -isopropylacrylamide/polyacrylic acid IPN microgels can efficiently absorb the common bactericidal and virucidal compound benzalkonium chloride. The particles can form a stable aqueous colloidal suspension or be used as building blocks for soft free-standing films. Both materials showed antiseptic efficacy on the examples of Bacillus subtilis and S. aureus , which was approximately equal to the commercial antibiotic. Such polymer biocides can be used as liquid disinfectants, stable surface coatings, or parts of biomedical devices and can enhance the versatility of the possible practical applications of polymer microgels.

The synthesis of glycoconjugates, lectin-specific polymers containing a carbohydrate ligand (spacered residue of N-acetyl-D-glucosamine, β-N-Gly-GlcNAc) has been carried out. Glyconanoparticles (glycol-NPs) containing a label detectable by means of spectrophotometry, silver nanoparticles, have been prepared on the basis of the glycoconjugates. Copolymers of maleic anhydride with ethylene or N -vinylpyrrolidone have been used as a carrier to introduce the carbohydrate ligand and a stabilizer of silver nanoparticles. Solutions of the glycoconjugates and the silver glyconanoparticles have been characterized by means of light scattering, UV-visible spectroscopy, and TEM. The interaction of the obtained glycoconjugates and silver glyconanoparticles with N-acetyl-D-glucosamine-specific lectins of Solanum tuberosum agglutinin (STA) and wheat germ agglutinin (WGA) has been investigated by means of light scattering and UV-visible spectro-scopy. The data obtained via these physical methods using the carbohydrate-containing derivatives labeled with silver nanoparticles have been in agreement. It has been shown that the glycoconjugates and silver glyconanoparticles based on more hydrophilic copolymer of maleic acid with N -vinylpyrrolidone are more sensitive than the respective systems based on more hydrophobic copolymer of maleic acid with ethylene. It has been also shown that the considered systems are more sensitive to the STA lectin than to the WGA lectin. The silver glyconanoparticles have allowed more accurate and reliable detection of the lectins by means of light scattering, as compared to the glycopolymer., Competing Interests: The authors declare that they have no conflicts of interest., (© Pleiades Publishing, Ltd. 2022, ISSN 0965-545X, Polymer Science, Series A, 2022, Vol. 64, No. 4, pp. 277–289. © Pleiades Publishing, Ltd., 2022.ISSN 0965-545X, Polymer Science, Series A, 2022. © Pleiades Publishing, Ltd., 2022.Russian Text © The Author(s), 2022, published in Vysokomolekulyarnye Soedineniya, Seriya A, 2022, Vol. 64, No. 4, pp. 267–279.)

Polymer stimuli-responsive microgels find their use in various applications. The knowledge of its internal structure is of importance for further improvement and expanding the scope. Interpenetrating network (IPN) microgels may possess a remarkable feature of strongly non-uniform inner architecture, even microphase separation, in conditions of a selective solvent. In this research, we, for the first time, use a combination of static light scattering (SLS) and small-angle X-ray scattering (SAXS) techniques to collect the structure factors of aqueous dispersions of poly(N-isopropylacrylamide)-polyacrylic acid IPN microgels on the broad scale ofqvalues. We study the influence of solvent quality on microgel conformations and show that in a selective solvent, such a system undergoes microphase separation: the sub-network in a poor solvent conditions forms dense small aggregates inside the large swollen sub-network in a good solvent. We propose the microstructured sphere model for the IPN microgel structure factor interpretation and perform additional analysis and verification through coarse-grained molecular dynamics computer simulations., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

The search for new environmental-friendly materials for energy storage is ongoing. In the presented paper, we propose polymer microgels as a new class of redox-active colloids (RACs). The microgel stable colloids are perspective low-viscosity fluids for advanced flow batteries with high volumetric energy density. In this research, we describe the procedure for the anchoring of 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl (4-amino-TEMPO) redox-active sites to the polymeric chains of water-soluble microgels based on poly( N -isopropylacrylamide)-poly(acrylic acid) interpenetrating networks. Using cyclic voltammetry and EPR spectroscopy, we show that ca. 14% of 4-amino-TEMPO groups retain electroactive properties and demonstrate the reversible redox response. It allows achieving a stable capacity of 2.5 mAh/g, enabling the low-viscous catholyte with a capacity of more than 100 mAh/L.

A series of industrial chitosans were analyzed on the presence of residual heavy metals. For the first time, optical microscopy data showed that chitosan solution retained a huge number of insoluble microparticles while transmittance electron microscopy revealed that insoluble fibrous microparticles were incrusted by crystalline nanoparticles with the sizes 5-50 nm. A series of filters used for chitosan solution filtration was analyzed on the presence of retained heavy metal and other residuals by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDXS) and mass-spectrometry with inductively coupled plasma (ICP-MS) methods. The SEM-EDXS analysis revealed the presence of Fe residuals together with Si, Al, N and S in the particles found on the filters. ICP-MS analysis found the presence of heavy metals (mainly Fe, Cr and Ni) both on the filter surfaces and in the effluent chitosan solution passed though the filters. This study draws attention to the necessity of a careful selection of industrially manufactured chitosan in order to avoid hidden undesirable effects of chitosan on pharmaceuticals and biomaterials and gives a warning of inapplicability of a stainless-steel made apparatus as a reactor susceptible to caustic soda corrosion for chitin deacetylation and production of medical and food grade chitosan., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Oligochitosan (short chain chitosan) is more soluble in acidic aqueous media than a high molecular weight (MW) chitosan, but its antimicrobial activity decreases with increase in degree of acetylation (DA) and increase in pH above a critical pH threshold point. In the present study, oligochitosans varying in MW were additionally N-acetylated and their self-assembly properties and antibacterial activity toward Staphylococcus aureus and Escherichia coli were investigated in a wide pH range as a function of MW and DA. Light scattering studies reveals that reacetyleted oligochitosan with M w ≤ 11 kDa is completely soluble in alkaline media (up to pH 12.5), if its DA is not less than 16%. Reacetylated chitosans with DA ∼ 30% are solubile in the entire pH range up to 12.5, if their M w is not higher than 25 kDa, but they aggregate and precipitate from the solution at pH ≥ 8 when their M w is above 25 kDa. Considering the influence of DA and MW, the antibacterial activity of reacetylated oligochitosans is maximal in the short interval of DA 16-28% at pH 7.4. These results are promising for expanding practical application of oligochitosan in pharmaceutical, cosmetic, and food compositions.

Light scattering studies indicate that oligochitosan (short-chain chitosan) solutions contain aggregates at pH values below the critical pH of phase separation, while at or above this point the gel phase coexists with the aggregate solution. This work demonstrates for the first time that the presence of D-glucosamine in an oligochitosan solution shifts the critical pH to a higher value and improves the oligochitosan antibacterial activity against Escherichia coli, Staphylococcus aureus, and Staphylococcus epidermis in neutral and slightly alkaline aqueous media. By comparing the results of light scattering studies and antimicrobial assays one can conclude that the antimicrobial activity of oligochitosan is dependent on its unimolecular form, not its supramolecular structures. The widening of the homogeneity region of an oligochitosan solution could lead to promising biomedical applications., (Copyright © 2013 Elsevier Ltd. All rights reserved.)