Biopolymeric Materials Based on Carboxymethylated Starch

 

Olena Ishchenko1, Viktoriia Plavan1, Daria Kuchynska1*, Virgilijus Valeika2,

Jolita Ostrauskaite2, Igor Okhrimenko1

1Department of Chemical Technologies and Resource Saving,

Kyiv National University of Technologies and Design, Kyiv, Ukraine.

2Department of Polymer Chemistry and Technology, Kaunas University of Technology, Kaunas, Lithuania.

*Corresponding Author E-mail: dkuchinska@gmail.com

 

ABSTRACT:

Biopolymers, including polysaccharides, have received great attention for their such beneficial characteristics as biodegradability, lack of toxicity, safety, availability, and low cost. However, biopolymers are susceptible to microbial contamination when exposed to the external environment. A polymer blend for obtaining films from Carboxymethylated Starch (CMS) and Gelatin, with the addition of decamethoxine (DKM) as an antiseptic drug by the solution-casting method, is proposed. The effect of the DKM on changes in the properties of films has been investigated. DKM release into the aqueous phase is most intense during the first 30 min, and then the process slows down. At the same time, the complete dissolution of the films occurred after almost 4 hours. The desired rate of DKM release can be ensured by adjusting the ratio between CMS and gelatin amount in the film. The method of FTIR spectroscopy revealed that the interaction between polymers and DKM is possibly accompanied by forming a chemical bond between the oxygen atom of the carboxyl group from CMS and the nitrogen atom from DKM. The films based on CMS /Gelatin 50/50% wt. with a DKM solution`s content of 5% can be recommended for further research to develop coatings for wounds of various origins.

 

KEYWORDS: Carboxymethylated starch, Gelatin, Decamethoxine, Moisture absorption, Drug release, Polymer films.

 

 


INTRODUCTION: 

In modern circumstances, injuries to the extremities make up 53-70% of total injuries. Injuries to limbs are notable for their complexity, multiplicity, and combined damage to soft tissues and bones, frequently involving major blood vessels and nerve trunks, as well as limb avulsion.1

 

Treatment begins with a primary dressing to protect the wound from the environment and microbial contamination. This dressing also helps drain wound fluid and partially remove small particles. The core of surgical treatment involves early and thorough primary surgical intervention, using antiseptics and antibacterial medications.2 Antiseptics are frequently used to prevent and treat local infectious diseases and sepsis. In the 1980s and 1990s, the use of antiseptics significantly increased in many clinics. The prevention and treatment of local infections using antiseptic medicines is highly important.3

 

Over the past decades, domestic antiseptic drugs based on the substance Decamethoxine® have been developed, mass-produced, and introduced into medical practice in Ukraine. Numerous studies have proven the high antibacterial efficacy of 0.02% Decamethoxine® against pathogens of infectious disease.4 A comparative study of the antimicrobial activity of antiseptics from the quaternary ammonium compounds showed high efficacy of Decamethoxine® 0.02% against Staphylococci, Streptococci, Enterococci, Salmonellae, Escherichia, Proteus, Spore-Forming Microorganisms, Yeast-Like Fungi, Influenza Viruses, Trichomoniasis Pathogens, and S. aureus.5-6 Natural polymers such as proteins and polysaccharides have attracted significant attention due to their beneficial properties such as non-toxicity, safety, biodegradability, availability, and low cost.7 Polysaccharides are widely used in many industries, especially in the pharmaceutical sector, where they serve as polymer matrices, emulsifiers and gelling agents, drug release agents and plasma substitutes.8

 

Proteins and their derivatives also play their role in the pharmaceutical industry particularly collagen9, gelatin10, silk fibroin11, and wheat gluten. Commercially available collagen for biomedical applications is mainly extracted from bovine or porcine skin. However, these collagen-based biomaterials demonstrate mild immunogenicity, high costs, variable physical and chemical properties and the risk of infectious disease transmission.12 When compared to collagen, the advantages of gelatin are better solubility and low antigenicity.13 Gelatin, a protein derived from the denaturation of collagen, is commonly used for pharmaceutical and medical applications due to its biodegradability and biocompatibility in physiological environments.14 Additionally, several chemical reactions have been applied to covalently crosslink gelatin.15,16,17 Recently, blends have been developed for use as medical capsule materials.18

 

The goal of this study is to investigate blends of starch or carboxymethylated starch (CMS) with gelatin (Gel) to develop films containing decamethoxin as a basis for drug delivery systems designed to prevent and treat local infections caused by gunshot wounds.

 

MATERIALS AND METHODS:

Materials:

The materials used for the formation of compositions and films: corn starch (Merck, Germany) CAS 9005-25-8 (СS), carboxymethylated starch (Aschem GmbH , Switzerland, the content of the active substance is not less than 75.0%) CAS 9057-06-1 (CMS) (Figure 1a), glycerol (BASF,  Germany), Gelatin (Trobas  Gelatine BV, Netherlands, the content of the active substance is not less than 99.8%), CAS 9000-70-8 (Gel); antiseptic drug decamethoxine 10-[dimethyl-[2-(5-methyl-2-propan-2-ylcyclohexyl)oxy-2-oxoethyl] azaniumyl] decyl-dimethyl-[2-(5-methyl-2-propan-2-ylcyclohexyl)oxy-2-oxoethyl]azanium dichloride (DKM) CAS 32726-24-2 (Figure 1b).

 

 

Figure 1. Chemical structure of (a) carboxymethylated starch;19 (b) decamethoxine.20

 

We used the pharmaceutical drug Dekasan, manufactured by YURiA-PHARM LLC, Ukraine. This drug contains 0.2mg of the active pharmaceutical ingredient (API) decamethoxine (DKM) in 1ml of solution (based on dry matter).

 

DKM, the product (registration certificate is UA/12128/01/01) of the Institute of Organic Chemistry of the National Academy of Sciences of Ukraine is easily soluble in water (pH of the solution is in the range of 5.5- 7.5) and 96% alcohol. It shows activity against gram-positive and gram-negative bacteria such as Staphylococci, Streptococci, Diphtheria and Escherichia Coli, Salmonella, Proteus, Klebsiella, Shigella, Pseudomonads, Clostridia and yeast or mold fungi19. Usually is used 0.02% solution of DKM.20-22

 

Preparation of the Polymers Solutions:

a)   Preparation of the starch solution:

The starch solution was prepared by stirring and heating a mixture of 10.0g of dry starch with cold distilled water (90.0g) on a water bath from 85 to 90°C for 15-20min until it thickened and formed a homogeneous transparent mass, which was cooled to ambient temperature.23

b) Preparation of the carboxymethylated starch solution:

Carboxymethylated starch solution was prepared by adding 10.0g of dry carboxymethylated starch to 90.0g of distilled water (temperature 20 to 22°C) and stirring the mixture for 15 min until thickened and a homogeneous clear mass was formed.

 

Preparation of the gelatin solution:

For gelatin swelling in the distilled water, pour demineralized water on top of the 10g gelatin until 100 ml is reached. Before use, the gelatin needs to be dissolved by raising the temperature to 40oC. Stir occasionally until the gelatin is fully dissolved.

 

 

 

Preparation of the Mixture of Polymer Solutions with decamethoxine:

The prepared solutions of starch or carboxymethylated starch and gelatin were mixed in a ratio of 25:75, 50:50, 75:25 wt. % and 1, 3, 5 wt. % of decamethoxine solution.  The solution of DKM was added to the mixture of starch or carboxymethylated starch and gelatin solutions. The amount of added DKM solution was from 1 to 5% based on the dry mass of polymers in the mixture. All formed mixtures were supplemented by 2% (% based on mass of dry polymer) of glycerol as a qualitative plasticizer suitable for polymer blends.24

 

Determination of the Viscosity:

A Brookfield Model DV-III+ programmable rheometer (speed from 10 to 230 s-1) with a built-in Brookfield TC 200 thermostat (both Brookfield Engineering Laboratories, Inc., USA) was used to determine the viscosity of polymer solutions. For the test, aqueous solutions of gelatin, CS, CMS and their mixtures were prepared in polysaccharide/gelatin ratios of 25:75, 50:50, 75:25 and the determination was performed at 20 °C.

 

Methodology for Studying the Viscosity for the Solution Mixtures of starch or CMS with gelatin:

The viscosity of solutions based on starch and CMS with gelatin is subject to the power law and is characterized by the Ostwald-de-Waele equation (1):

𝜂 = K 𝛾n−1                                                                                    (1)

 

where  K is the consistency index, γ is the shear rate, ann is the flow behaviour index. The parameters K and n characterize the rheology of power-law fluids. The flow behaviour index n is dimensionless; for pseudoplastic fluids n<1. When n>1, the fluid is dilatant rather than pseudoplastic.25

 

As a result of mathematical processing of experimental data obtained from determining the viscosity for blends solutions of starch or CMS with gelatin, the values of the constants K and 𝜂 were obtained from equation 1 (Table 1). Then, using formula (2), the degree of thixotropic recovery of the solution viscosity was calculated.26

 

                             (2)

 

𝜂0i – the viscosity at the i-th shear rate, measured in the mode of the increasing shear rate gradient, Pa۰s; 𝜂1i – the viscosity at the i-th shear rate, measured in the mode of the decreasing shear rate gradient, Pa۰s; i – shear rate; n – the number of fixed values of the shear rate gradient; S – the degree of thixotropic recovery of the solution viscosity, %.

Preparation of the Films and Determination of Their Properties:

a) Preparation of the Films:

The casting solution method was used to prepare the films. It was carried out as follows: 50ml of film-forming solution was poured onto the polypropylene surface (100 × 200mm). The films were dried in an oven at 40°C for 90min and then dried at ambient temperature for 24h. The CMS/Gelatin-based films had a yellowish colour and were flexible.

 

b) Determination of Moisture Absorption by the Films:

Moisture absorption was evaluated by the increase in sample mass, compared with the initial dry mass, and expressing the increase as a percentage of dry mass.26 To determine the moisture absorption of films, samples (size 10 × 10mm and thickness 0.06mm) without visible surface defects, pre-dried at 105°C for one hour, cooled to ambient temperature, and weighed to the nearest 0.001g were used.

 

For the test, the samples were placed (hung) in glass beakers filled with distilled water (temperature 20-22 °C) so that the samples had no contact with the beaker walls and the distance to the walls was at least 10mm. The distance between the surface of the water and the top edge of the sample should be at least 10mm.

 

c) Determination of the Tensile Strength and Relative Elongation of the Films:

The tensile strength and relative elongation at break were determined according to the ASTM D882-18 Standard Test Method for Tensile Properties of Thin Plastic Sheeting.27 Tensile tester BDO–FBO.5TH (ZwickRoell, Germany) was used.

 

To assess the effect of humidity on the mechanical properties of the film, the samples were pre-dried at 105°C for one hour and cooled to ambient temperature. The films were then placed for 24h in desiccators with relative humidity of 45, 65 and 80% (temperature 20-22 °C). Strips of 150 × 10mm were then cut from the films and tested.

 

Determination of decamethoxine content in the solution:

Determination of decamethoxine content in the solution was carried out in accordance with the pharmacopoeial article FS 42U-46-152-97 Decamethoxine.28 To determine the content of decamethoxine in the solution, a basic decamethoxine solution with a concentration of 0.1g/l is prepared. To do this, carefully weigh 0.05g of DKM (exact mass) based on dry matter, place in a 500 ml volumetric flask, dissolve in a small amount of water, and bring the volume of the solution to the mark and mix.

To construct a calibration curve, a series of solutions was prepared. For this purpose, 1.0; 2.0; 3.0; 4.0; 5.0; 6.0; 7.0; 8.0; 9.0; 10.0ml of the basic solution of decamethoxine were placed in 25ml volumetric flasks, 2 ml of 0.1% polyvinyl alcohol solution, 1ml of 0.07% eosin solution, 1.5ml of 0.05M hydrochloric acid solution were added to each volumetric flask, then water was added to the mark and mixed (solution A).

 

The decamethoxine has a very specific absorption at 540 nm, allowing direct measurement of the decamethoxine concentration.29 The optical density of solutions A was measured on an OPTIZEN POP UV VIS spectrophotometer («Mecasys», South Korea) at a wavelength of 540nm in a cuvette with a layer thickness of 10mm. For comparison, solution B was used, prepared similarly to solution A, but without adding decamethoxine. A calibration curve has been constructed (Figure S1).

 

Determination of the Decamethoxine content during Dissolving the Films and kinetic of Decamethoxine release:

The kinetics of decamethoxine release was assessed by the analytical method according to the pharmacopoeial method “Dissolution test for transdermal patches”, 30 using a UV-VIS OPTIZEN POPUVVIS spectrophotometer (Mecasys, South Korea).

 

The dissolution of films with decamethoxine was carried out in a VK 7000 dissolution tester with a VK 750D water heater (Vankel, USA), at a temperature of 32(±0.5)0C and a rotation speed of 100rpm. The volume of the dissolution bowl was 250ml and the diameter of the disc was 8.5mm. Purified water was used as the dissolution medium.

 

First, each film sample was weighed. During the film dissolution in water, an initial water sample was taken and then every 30minutes until the beginning of the destruction process of the film samples, which occurred after 230minutes. The volume of the sample solution was 5 ml. A similar volume of water was added to correct the volume losses.

 

The content of DKM in aqueous solution was determined spectrophotometrically using the OPTIZENPOP UV-VIS (Mecasys, South Korea) at a wavelength of 540 nm. Quantitative determination of decamethoxin content was performed according to the method described in paragraph 2.6. The DKM content (mg/ml) was calculated by the formula (3):

 

                              (3)

 

where D1 – optical density of the studied solution; D0 – optical density of the DKM basic solution; m0 – film mass, g; V1 – volume of the studied solution, 25ml; V2 – volume of the dissolution vessel, 250ml; V3 – volume of the studied sample (ml), V3 = 5ml; V4 – volume of solution A, 25ml.

 

The reaction rate of decamethoxin release was determined by formula (4):

 

                                                              (4)

 

where KR is the rate of decamethoxin release, s–1; C1, C2 – concentration of the released substance during time t1, t2 ….. ti; release time t1, t2 – s. Based on the obtained results, the dependencies of the concentration of decamethoxine in the aqueous medium on the duration of the release were constructed (Fig. 6). The obtained results did not contradict the results of other authors.31  We came to the conclusion that the process of release of decamethoxine into the water environment can be described by a first order kinetic model (Fig. 6). After establishing the release rate of decamethoxine, the first-order rate constant was determined according to formula (5):

 

                                              (5)

 

where k1 – first-order constant; C0 – an initial concentration of decamethoxin released; Ct – the concentration of decamethoxin released in the time.32

 

IR spectroscopy:

For IR spectroscopy a Fourier transform infrared Perkin Elmer PARAGON 1000 PC spectrometer (wavelength range 400-4000 cm-1) was used. The test samples were thoroughly crushed and pressed into tablets with KBr.

The assignment of absorption bands in the infrared spectra of the studied materials (gelatin, polymers) to certain types of compounds (groups of atoms) was determined based on work in the field of infrared spectroscopy. 33,34,35,36,37

 

Statistical analysis:

All data were expressed as the average value of measurements performed in triplicate. One sample was used for one measurement. The statistical analysis was performed using STATISTICA10. A p-value of less than 0.05 was considered statistically significant for all analyses.

 

RESULT:

Rheology of polysaccharide solutions:

The first step was to evaluate the viscosity of solutions of various biopolymers and their compositions. The results presented in Figure 2 show the dependence of the viscosity of solutions of polymeric compositions based on starch with gelatin on the shear rate gradient.

 

 

Figure 2. Dependence of the viscosity of the Starch/Gelatin based solution on the shear rate.

 

The viscosity of polymer solutions is usually higher than that of low molecular weight compounds. Only very diluted solutions of the macromolecular compounds behave like Newtonian fluids. The high viscosity of diluted solutions of the macromolecular compounds is due to the peculiarities of the hydrodynamics of systems containing long and flexible macromolecules.38 This statement is supported by the fact of interaction between starch and gelatin, in particular proven by the authors of the article.39

 

As shown in Figure 2, an abnormal decrease in viscosity occurs with increasing shear rate, indicating pseudoplastic properties of solutions of polymer compositions. At high strain rates, the particles become oriented, stretched, deformed or disintegrated, which affects the apparent viscosity (in these cases, shear thinning is the main phenomenon).40

 

Figure 3 shows the dependence of the viscosity of the CMS/ Gelatin based solutions on the shear rate gradient. With an increase in shear rate, an abnormal decrease in viscosity also occurs. For polymer composition solutions of Starch/Gelatin, a decrease in viscosity is observed compared to starch solutions (Figure 2).

 

 

Figure 3. Dependence of the viscosity of the CMS/Gelatin based solution on the shear rate.

For polymer composition solutions of CMS/Gelatin, an increase in viscosity is observed compared to CMS solutions (Figure 3). The presence of carboxyl groups in the carboxymethylated starch molecule probably causes a more intense interaction between gelatin and carboxymethylated starch.

 

The constants К and n of the equation (1) were determined for solutions of starch41, carboxymethylated starch and gelatin and their compositions with different polymer ratios (Table 1). With an increase in the content of CMS up to 75wt. % in the polymer composition solution, an increase in the flow index n is observed, which indicates a decrease in the structure of the system and a low degree of pseudo-plasticity. 

 

Table 1. Values of  К and n constants and of the equation (1) for solutions of polysaccharides with gelatin.

Composition of 10 % solutions

К, Pа∙s

n

Gelatin

9.098

0.81

Starch

16.051

0.56

Starch/ Gelatin (25/75)

11.577

0.67

Starch/ Gelatin (50/50)

10.866

0.76

Starch/ Gelatin (75/25)

13.179

0.66

CMS

15.912

0.01

CMS/ Gelatin (25/75)

9.136

0.78

CMS/ Gelatin (50/50)

9.210

0.77

CMS/ Gelatin (75/25)

8.186

0.83

 

The determined thixotropy degree indicators, calculated using formula (2), for polymeric compositions based on starch and CMS with gelatin, as well as the pure components, are given in Table 2. A high degree of thixotropic viscosity recovery was found in almost all solutions of polymeric compositions. Moreover, with a decrease in the CMS content in polymeric compositions based on CMS/Gelatin, the degree of thixotropic viscosity recovery increases from 86 to 96%, which confirms the fact of the interaction of polymer macromolecules due to the functional groups of carboxymethylated starch.

 

Table 2. Degree of thixotropic viscosity recovery.

Composition

Degree of thixotropy, %

Gelatin 10%

70.0

CMS, 10 wt.%

81.0

Starch 10%

54.0

Starch/ Gelatin (25/75)

88.0

Starch/ Gelatin (50/50)

89.0

Starch/ Gelatin (75/25)

90.0

CMS/ Gelatin (25/75)

96.0

CMS/ Gelatin (50/50)

88.0

CMS/ Gelatin (75/25)

86.0

 

Thus, according to the results of rheological studies, it was found that CMS-based polymer compositions retain their stable thixotropic characteristics and can be recommended for obtaining films of a given thickness by the solution-casting method.

Moisture absorption properties of the polysaccharides-based films and their mechanical strength:

From the presented data on the kinetics of water absorption of the films (Figure 4), it was found that the studied samples of Starch/Gelatin and CMS/Gelatin belong to limited swelling systems by the nature of the curves.

 

An increase in the gelatin content in films based on both CMS and starch is accompanied by an increase in water absorption, although for films based on the CMS/Gelatin composition, the value of the water absorption index is higher, particularly, at a gelatin content of 75%, the water absorption reaches 340%. After 40 minutes, because of the swelling of the film, the first signs of its destruction appeared which made it impossible to weigh it. When the film is watered down, the antimicrobial agent is gradually released from the polymeric material and actively acts on microorganisms, preventing their growth and development. In addition, the presence of free carboxyl groups increases the antimicrobial activity of the polymeric material itself, as the pH of the medium decreases, which creates unfavourable conditions for the vast majority of microorganisms. Therefore, CMS/Gelatin-based films were used to determine the effect of DKM on the properties of polymeric systems.

 

 

Figure 4. Kinetics of moisture absorption of films based on starch or carboxymethylated starch with gelatin.

 

From the analysis of the mechanical properties of CMS/Gelatin-based films (Figure 5), it was found that with an increase in the CMS content from 25 to 50%, the tensile strength of the film increases by a factor of 3, depending on the film moisture content (from 6.12 to 18.6 MPa at a moisture content of 45%; from 9.18 to 27.9 MPa at a moisture content of 65%). At 80% moisture content, the tensile strength of films with 25-50% CMS content ranges from 27.6-33.3 MPa. An increase in the CMS content to 75% is accompanied by a decrease in the tensile strength of the film at any moisture content.

 

Figure 5. Tensile strength of CMS/Gelatin-based films with 45, 65 and 80% moisture content.

 

As it can be seen from the above data, an increase in film moisture content contributes to an increase in its tensile strength. The effect of moisture in the film on mechanical properties is dual in nature.42,43,44 On the one hand, moisture acts as a plasticiser, which increases the flexibility of the film due to its ability to destroy internal hydrogen bonds between polymer chains while increasing the molecular space.45 This facilitates the orientation of the polymer chains in the tensile direction and increases the tensile strength. On the other hand, the hydrolytic cleavage of bonds due to the plasticiser can reduce the value of the fracture stress.46

 

The addition of DKM solution to the polymeric compositions CMS/Gelatin 25/75 and 75/25% wt. has almost no effect on the tensile strength of the film. The addition of DKM solution to the polymeric composition CMS/Gelatin 50/50 reduces the tensile strength from 18.6 to 3.26 MPa for samples with 45% moisture content, from 27.9 to 7.62 MPa for samples with 65% moisture content, and at 80% moisture content the tensile strength did not change significantly with the addition of decametoxine.

 

Thus, CMS/Gelatin-based films of 50/50% wt. by the results of their strength and moisture absorption capacity demonstrate the properties required for a polymeric carrier of APIs and can be recommended for further research.

 

The kinetics of drug release:

One of the most important stages of drug development is the selection of a polymeric material for the base, which will determine its pharmacotherapeutic properties: the kinetics of API release from the polymeric base, its dissolution, and penetration into skin lesions. The influence of the polymer composition on the kinetics of DKM release from the polymer film into the aqueous phase was studied depending on the composition of the CMS/Gelatin-based film (25/75; 50/50; 75/25) at a DKM solution content from 1 to 5% Figure 6 shows the influence of DKM solution`s content in CMS/Gelatin-based films (50/50) on its release into the aqueous phase.  Similar dependences are observed for other films.

 

 

Figure 6. Influence of DKM solution`s content in CMS/Gelatin-based films (50/50) on its release into the aqueous phase

 

The release of DKM into the aqueous phase is most intense during the first 30 min, then the process slows down. At the same time, complete dissolution of the film occurred after almost 4 hours.

 

During the experiment, the average value of the release rate constant k1 was determined according to the first-order kinetic model for CMS/gelatin polymer systems. (Figure 7). For CMS/Gelatin-based films (50/50), the highest DKM release rate was observed at a content of 3 wt.%, which is described by a first-order rate constant of 0.011 seс-1. The lowest DKM release rate of 0.00047 seс1 at a content of 5 wt.% was also observed for CMS/Gelatin-based films of 50/50 wt.%.

 

 

Figure 7. Average value of DKM release rate constants for the CMS/Gelatin-based film.

 

The slow release of DKM will contribute to the prolonged action of the drug, so films based on CMS/Gelatin 50/50 wt.% with a DKM content of 5% can be recommended for further research to obtain coatings for wounds of various origins and for the polymeric base of drug carriers in transdermal therapeutic systems.

 

FTIR spectroscopy results:

The type of chemical bonds between CMS and DKM formed as a result of their interaction was determined by infrared spectral analysis. The FTIR spectra of CMS/Gel films with or without DKM are presented in Figure 8. Interpretation of infrared spectra was carried out taking into account the characteristic frequencies of pure decamethoxine.46

 

 

Figure 8. FTIR spectra of the CMS/Gelatin-based films (50/50) with DKM solution (5 wt.%).

 

As shown in Figure 8, the special pattern, typical for native starch in the region of 1000 cm -1 and 1200 cm -1 is preserved in CMS.47  The bands located at 1014 cm−1, 1075 cm−1, and 1160 cm−1 correspond to –C–O–C– bonds in the anhydroglucose unit in CMS. The bands at 1160 and 1075 cm-1 were related to the ordered structures of CMS, whereas the band at 1014 cm-1 is associated to the amorphous structures of CMS.48 The absorption peak at 1654 cm-1 corresponds to the bending vibration peak of OH present in CMS.49 In case of CMS/Gel the broad band with a center about 3440 cm -1 corresponds to the stretching vibrations of OH group. The absorption band at 2900 cm–1 could be attributed to CH2 stretching vibrations. In case of CMS/Gel+DKM the absorption band of the δ –N+–CH2– group, which are characteristic of quaternary amine salts, is observed in the region of 1400-1440 cm-1. The absorption band at 872 cm−1 corresponds to asymmetric stretching vibrations of the group C-N+(CH3)3 which are also characteristic of quaternary amine salts.50.51 The absorption band 3070 cm–1 and the appearance of absorption bands at 716 cm−1, 747 cm−1, and 762 cm−1 the authors52,53,54 associate with the formation of the ionic complexes.

 

CONCLUSION:

As a result of the conducted research, a polymer mixture composition for obtaining films from Carboxymethylated Starch/Gelatin with the addition of decamethoxine as an antiseptic drug by solution-casting method is proposed. It was established that the content of CMS up to 50 wt.% in the presence of gelatin increases the mechanical strength of materials.

 

The solutions of CMS/gelatin were found to belong to abnormally viscous structured systems (n < 1), characterised by a sufficiently high degree of thixotropic viscosity recovery (86-96%), which is associated with the low structuredness of the studied solutions. DKM release into the aqueous phase is most intense during the first 30 min, then the process slows down with the polymer composition of the film significantly affecting the release kinetics. At the same time, complete dissolution of the film occurred after almost 4 hours. The lowest DKM release rate of 0.00047 sec-1 at a content of 5 wt.% is observed for films of CMS /Gelatin 50/50 wt.%.

 

The method of FTIR spectroscopy revealed that the interaction between CMS and API is possibly accompanied by forming a chemical bond between the oxygen atom of the carboxyl group from carboxymethylated starch and the nitrogen atom from decamethoxin. The ability to form a relatively strong bond between CMS and decamethoxine in the film likely enables the gradual release of the API into solution upon wetting of the film. The desired rate of decamethoxine release can be achieved by optimizing the ratio of carboxymethylated starch to gelatin in the film and considering the content of decamethoxine.

 

The films based on CMS /Gelatin 50/50% wt. with a DKM content of 5% can be recommended for further research as potential wound coatings for various types of injuries. Based on the antibacterial properties of decamethoxine provided by its manufacturer, it can be concluded that these films can effectively protect wounds from external influences. Additionally, the presence of decamethoxine will inhibit the activity of pathogenic microorganisms that may enter the wound before first aid is administered.

 

CONFLICT OF INTEREST:

The authors have no conflicts of interest regarding this investigation.

 

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Received on 31.08.2025      Revised on 29.12.2025

Accepted on 02.03.2026      Published on 01.07.2026

Available online from July 04, 2026

Research J. Pharmacy and Technology. 2026;19(7):3075-3083.

DOI: 10.52711/0974-360X.2026.00437

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