CC BY
354
CHEMICAL SCIENCES / «COLLOMUM-JMTMaL» #121171), 2023
CHEMICAL SCIENCES
UDC: 577.352.2
Lebedev Vladimir Vladimirovich
Ph.D. in technical sciences, Assistant Professor, Assistant Professor of the department ofplastics and biologically active polymers technology, National Technical University «Kharkiv Polytechnic Institute»
Miroshnichenko Denis Viktorovich
Doctor of Technical Sciences, professor, chair of the department of oil, gas and solidfuel refining technologies National Technical University «Kharkiv Polytechnic Institute»
Lebedeva Katerina Oleksandrivna Ph.D. student of the department ofplastics and biologically active polymers technology, National Technical University «Kharkiv Polytechnic Institute» Cherkashina Anna Mykolaivna
Ph.D. in technical sciences, Assistant Professor, chair of the of the department ofplastics and biologically active polymers technology, National Technical University «Kharkiv Polytechnic Institute»
Kariev Artem Igorovich
Ph.D. in technical sciences, O.M. Beketov National University of Urban Economy in Kharkiv, Kharkiv,
Ukraine
DOI: 10.24412/2520-6990-2023-12171-54-57 BROWN COAL HUMIC SUBSTANCES HYBRID MODIFIED BIOLOGICALLY ACTIVE POLYMERIC HYDROGEL MATERIALS RESEARCH
Abstract
A paper deals with biologically active polymeric hydrogel materials. Literature review was carried out and it was proved that humic acids using is perspective for the functional effect on the hydrogel biopolymer materials properties. Structuring processes and strength characteristics improving are the most changeable while using humic acids. Biologically active polymer hydrogel materials based on gelatin and sodium alginate, modified with lignite humic acids were designed and produced. The peculiarities impact of the received humic substances conditions from brown coal on their qualitative and quantitative composition were determined. By carrying out rheological, conductometric and microscopic studies, it was found that the modification of gelatin-sodium alginate systems with humic acids allows receive polymer hydrogels with high structuring degree. It has been found that effective processes for receiving biologically active polymer hydrogel materials based on gelatin and sodium alginate can be carried out in different humic acids concentration values while achieving an increase in hydrogel polymers structuring processes. It was found that the humic substances optimal content in gelatin-sodium alginate systems is no more than 5% by weight.
Keywords: humic acid, brown coal, biologically active, materials, hydrogel, polymer, gelatin, sodium algi-
nate
Introduction
The modern trend in biologically active polymers advancement and materials based on them is the making effective systems for drugs and active substances delivery into the human body [1]. Biologically active polymeric materials for delivery systems are patches and plasters that contain active substances [2].
Polymers used to make bioactive polymer materials for drug delivery systems in the patches form must be water-soluble, biocompatible, and mechanically strong for dermal introduction [3]. The most common method of biologically active polymer materials production for delivery systems in the patches form is the solvent casting method. Due to their high efficiency, biologically active polymer materials for delivery systems in the patches form based on biopolymer hydrogels are most widely used today. The delivery mechanism in such polymer hydrogel patches is based on the fact that active substances in the hydrogel is delivered to the skin by diffusion [4,5]. The most effective modern hydropolymeric patches made of hydroxypropyl-methylcellulose [6], hyaluronic acid [7], carboxyme-thyl cellulose [8], polyvinylpyrrolidone [9] and pol-ylactic glycolic acid [10]. In polymer hydrogel
biologically active delivery systems, the active substance is contained in all patch areas, the main substrate and the backing of the patch or plaster and is released at a slow rate while the patch is applied to the skin.
In our previous works, it was determined that hu-mic substances have a functional effect on the hydrogel biopolymer materials based on gelatin and hydroxypro-pyl cellulose properties, especially for increasing structuring processes and strength characteristics [11, 12]. Therefore, it is interesting to study the possibilities of effective modification of biologically active polymer hydrogel materials based on gelatin and sodium algi-nate with humic substances for receiving systems for drugs and active substances delivery into the human body.
The aim of the article is brown coal humic substances hybrid modified biologically active polymeric hydrogel materials research.
Raw materials and test methods
The study's objects were:
- food gelatin brand R-11 (Ukraine);
- sodium alginate (China);
- humic acid, were received by extraction from brown coal.
Conductometric studies of polyvinyl alcohol solutions were carried out on a combined TDS-meter HM digital COM-IOO (USA), scale range: specific conductivity: from 0 to 9990 mkS/cm; temperatures: from 0 to 55 °C; Error: ± 2%.
Microscopic studies were carried out using the electron microscope Digital Microscope HDcolor MOS Sensor (China).
The viscosity was determined according to ISO 2431. The method is based on determining the viscosity of a solution with free flow is taken as the time of continuous flow in seconds of a volume of 50 cm3 of the test material through a calibrated nozzle with 4 mm diameter of a VZ-246 viscometer at a certain temperature.
Brown coal humic substances hybrid modified biologically active polymeric hydrogel materials received in the following way. First, a gelatin solution (7
Table 1
The conditional viscosity and conductivity dependence of biologically active polymeric hydrogel materials from gelatin, sodium alginate on the different humic acid content
% wt.), a defined amount of polymer was placed in 50 mL of distilled water (preheated at 90 ± 2oC) and stirred to obtain a clear solution. For the co-mixture of gelatin and sodium alginate, a defined amount of sodium alginate (2,5 % wt.) was added in the previously prepared gelatin (7 % wt.) solution and allowed to mix homo geneously on a Magnetic Stirrer with Heating Plate VEVOR 85-2 (United Kingdom). After that, by mixing, solutions with humic acids were obtained, in which the concentration of the latter was 5, 10 and 15 % wt.
Results and discussion
The conditional viscosity and conductivity dependence of biologically active polymeric hydrogel materials from gelatin, sodium alginate on the different humic acid content is shown in table 1.
Sample Humic acid content, % wt.) v, s ^ , mkS/cm
Gelatin-sodium alginate hydrogel 114 2350
5 128 2650
Humic acid 10 25 3450
15 - 3610
Hydroxypropyl methylcellulose- sodium alginate hydrogel 1200 1630
5 1350 2110
Humic acid 10 1400 2400
15 1650 2950
* v - conditional viscosity, s; ^ - conductivity, mkS/cm
It shows that the humic acids addition to the studied gelatin-sodium alginate systems leads to an increase in polymer structuring processes. Due to the significant structure formation processes intensification in gelatin-
sodium alginate systems, the specific electrical conductivity increases from 2350 to 3610 mkS/cm and intense polymer system agglomeration occurs, which can be seen from microscopic studies (fig. 1).
Figure 1. Microscopic studies of biologically active polymeric hydrogel materials: A - pure gelatin and sodium alginate hydrogel; B - gelatin and sodium alginate hydrogel + 5 % wt. of humic acid; C - gelatin and sodium alginate hydrogel + 10 % wt. of humic acid; D - gelatin and sodium alginate hydrogel + 15 % wt. of humic
acid.
It should be noted that when humic acids content greater than 5% wt. there is a hydrogel delamination in an aqueous phase and a structured polymer phase (fig. 1). Such structure formation regularities are well consistent with specifics change in conditional viscosity in gelatin-sodium alginate systems: it increases from 114 to 128 seconds up to 5 % wt. humic acids content, and then sharply decreases to 25 seconds when the humic acids content increases to 10% wt. due to the aqueous and polymer phases stratification.
So it was found that effective receiving processes of biologically active polymer hydrogel materials based on gelatin and sodium alginate can be carried out in different humic acids concentration while achieving an increase in the hydrogel polymers structuring processes. It was determined that the optimal humic substances content in gelatin-sodium alginate systems is no more than 5 % wt.
Conclusion
Biologically active polymer hydrogel materials based on gelatin and sodium alginate, modified with lignite humic acids, were received and researched. By carrying out rheological, conductometric and microscopic studies, it was found that the modification of gelatin-sodium alginate systems with humic acids allows receive polymer hydrogels with high structuring degree. It was determined that the optimal humic substances content in gelatin-sodium alginate systems is no more than 5 % wt. In future researching to determine
the most important transdermal characteristics of designed biologically active polymer hydrogels is very perspective.
List of references
1. Cabrera F.C. Eco-friendly polymer composites: A review of suitable methods for waste management. Polymer Composites, 2021. V. 42. P. 2653- 2677.
1. Altomare L., Bonetti L., Campiglio C.E., De Nardo L., Draghi L., Tana F., Farè S. Biopolymer-based strategies in the design of smart medical devices and artificial organs. The International Journal of Artificial Organs. 2018. V. 41(6). P. 337-359.
2. Kim S., Oh T., Lee H., Nam J. Trends and perspectives in bio- and eco-friendly sustainable nano-material delivery. systems through biological barriers. Materials Chemistry Frontiers. 2022. V. 6. P. 21522174.
3. Prausnitz M.R. Engineering microneedle patches for vaccination and drug delivery to skin. Annual Review of Chemical and Biomolecular Engineering. 2017. V. 8. P. 177-200.
4. Migdadi, E.M., Courtenay, A.J., Tekko, I.A., McCrudden, M.T., Kearney, M.C., McAlister, E., McCarthy, H.O., Donnelly, R.F.: Hydrogel-forming microneedles enhance transdermal delivery of metfor-min hydrochloride. Journal of Controlled Release. 2018. V. 285. P. 142-151.
5. Courtenay A.J., McAlister E., McCrudden M.T.C., Vora L., Steiner L., Levin G., Levy-Nissen-baum E., Shterman N., Kearney M.C., McCarthy H.O., Donnelly R.F. Hydrogel-forming microneedle arrays as a therapeutic option for transdermal esketamine delivery. Journal of Controlled Release. 2020. V. 322. P. 177-186.
6. Kim J.Y., Han M.R., Kim Y.H., Shin S.W., Nam S.Y., Park J.H. Tip-loaded dissolving microneedles for transdermal delivery of donepezil hydrochloride for treatment of Alzheimer's disease. European Journal of Pharmaceutics and Biopharmaceutics. 2016. V. 105. P. 148-155.
7. Du H., Liu P., Zhu J., Lan J., Li Y., Zhang L., Zhu J., Tao J. Hyaluronic acid-based dissolving microneedle patch loaded with methotrexate for improved treatment of psoriasis. ACS Applied Materials and Interfaces. 2019. V. 11. P. 43588-43598.
8. Mistilis M.J., Bommarius A.S., Prausnitz M.R. Development of a thermostable microneedle patch for influenza vaccination. Journal of Pharmaceutical Sciences. 2015. V. 104. P. 740-749.
9. Tang J., Wang J., Huang K., Ye Y., Su T., Qiao L., Hensley M.T., Caranasos T.G., Zhang J., Gu Z., Cheng K. Cardiac cell-integrated microneedle patch for treating myocardial infarction. Science Advances. 2018. V. 4(11) . P. 9365.
10. Li Y., Zhang H., Yang R., Laffitte Y., Schmill U., Hu W., Kaddoura M., Blondeel E.J.M., Cui B. Fabrication of sharp silicon hollow microneedles by deep-reactive ion etching towards minimally invasive diagnostics. Microsystems and Nanoengineering. 2019. V. 5. P. 41.
11. Lebedev V., Miroshnichenko D., Xiaobin Z., Pyshyev S., Savchenko D. Technological Properties of Polymers Obtained from Humic Acids of Ukrainian Lignite. Petroleum and Coal. 2021. V. 63(3) . P. 646.
12. Lebedev V., Sizhuo D., Xiaobin Z., Miroshnichenko D., Pyshyev S., Savchenko D. Hybrid Modification of Eco-Friendly Biodegradable Polymeric Films by Humic Substances from Low-Grade Meta-morphism Coal. Petroleum and Coal. 2022. V. 64(3). P. 539-546.
