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. 2023 Mar 21;15(6):1551.
doi: 10.3390/polym15061551.

Coating Methods of Carbon Nonwovens with Cross-Linked Hyaluronic Acid and Its Conjugates with BMP Fragments

Sylwia Magdziarz  1 , Maciej Boguń  2 , Justyna Frączyk  1
Affiliations

Coating Methods of Carbon Nonwovens with Cross-Linked Hyaluronic Acid and Its Conjugates with BMP Fragments

Sylwia Magdziarz et al. Polymers (Basel). .

Abstract

The cross-linking of polysaccharides is a universal approach to affect their structure and physical properties. Both physical and chemical methods are used for this purpose. Although chemical cross-linking provides good thermal and mechanical stability for the final products, the compounds used as stabilizers can affect the integrity of the cross-linked substances or have toxic properties that limit the applicability of the final products. These risks might be mitigated by using physically cross-linked gels. In the present study, we attempted to obtain hybrid materials based on carbon nonwovens with a layer of cross-linked hyaluronan and peptides that are fragments of bone morphogenetic proteins (BMPs). A variety of cross-linking procedures and cross-linking agents (1,4-butanediamine, citric acid, and BDDE) were tested to find the most optimal method to coat the hydrophobic carbon nonwovens with a hydrophilic hyaluronic acid (HA) layer. Both the use of hyaluronic acid chemically modified with BMP fragments and a physical modification approach (layer-by-layer method) were proposed. The obtained hybrid materials were tested with the spectrometric (MALDI-TOF MS) and spectroscopic methods (IR and 1H-NMR). It was found that the chemical cross-linking of polysaccharides is an effective method for the deposition of a polar active substance on the surface of a hydrophobic carbon nonwoven fabric and that the final material is highly biocompatible.

Keywords: BDDE; BMP fragments; carbon nonwoven; citric acid; coating; cross-linking; hyaluronic acid.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
1H NMR spectrum of unmodified HA in D2O. Spectrum recorded with MestReNova 9.0 software.
Figure 2
Figure 2
1H NMR spectra of native HA (top) vs. HA cross-linked with butanediamine (bottom).
Figure 3
Figure 3
1H NMR spectra of native HA (top) vs. HA cross-linked with citric acid via Procedure I (bottom).
Figure 4
Figure 4
1H NMR spectra of native HA (top) vs. HA cross-linked with 5% citric acid via Procedure II (bottom).
Figure 5
Figure 5
1H NMR spectra of native HA (top) vs. HA cross-linked with 20% citric acid via Procedure II (bottom).
Figure 6
Figure 6
1H NMR spectra of native HA (top) vs. HA cross-linked with BDDE (bottom).
Figure 7
Figure 7
FT-IR spectrum of native HA (black) vs. HA cross-linked with 1,4-butanediamine (red).
Figure 8
Figure 8
FT-IR spectra of the HA cross-linked with CA via both procedures (Procedure I—top one; Procedure II—bottom one). FT-IR spectrum of native HA (black) vs. HA cross-linked with 25% citric acid via Procedure I (top, red) and 20% citric acid via Procedure II (bottom, red).
Figure 9
Figure 9
FT-IR spectra of HA cross-linked with CA via Procedure II with different concentrations of the cross-linking agent. FT-IR spectrum of native HA (black) vs. HA cross-linked with citric acid via Procedure II: 5% (top, red) and 20% (bottom, red).
Figure 10
Figure 10
FT-IR spectrum of native HA (black) vs. HA cross-linked with 1,4-butanediol diglycidyl ether, BDDE (red).
Figure 11
Figure 11
IR spectrum for a carbon nonwoven fabric after treatment with hyaluronic acid without the cross-linking process.
Figure 12
Figure 12
IR spectrum for 0.5% hyaluronic-acid-coated carbon nonwoven samples cross-linked with citric acid of different concentrations (5%—black line; 20%—red line).
Figure 13
Figure 13
IR spectrum for 2% hyaluronic-acid-coated carbon nonwoven samples cross-linked with citric acid of different concentrations (black line: CA 5%, red line: CA 20%).
Figure 14
Figure 14
IR spectrum for hyaluronic-acid-coated carbon nonwoven samples cross-linked with BDDE.
Figure 15
Figure 15
Comparison of IR spectra obtained for carbon nonwovens coated with hyaluronic acid at concentrations of 0.5% (top), 1% (center), and 2% (bottom) and cross-linked with different cross-linking agents (5% CA—black line; 20% CA—red line; BDDE—blue line).
Figure 15
Figure 15
Comparison of IR spectra obtained for carbon nonwovens coated with hyaluronic acid at concentrations of 0.5% (top), 1% (center), and 2% (bottom) and cross-linked with different cross-linking agents (5% CA—black line; 20% CA—red line; BDDE—blue line).
Figure 16
Figure 16
Schematic reaction of the condensation of carboxyl groups of polysaccharides with amino groups of H-KRMVRISRSL-OH by using EDC/NHS.
Figure 17
Figure 17
IR spectrum of native HA (black line) vs. HA–KRMVRISRSL conjugate (red line) and the spectrum of the used peptide (blue line).
Figure 18
Figure 18
MS spectrum of the obtained polysaccharide–H-KRMVRISRSL-OH conjugate.
Figure 19
Figure 19
MS spectrum of the native hyaluronic acid.
Figure 20
Figure 20
Schematic reaction of the polysaccharide–peptide condensation by using DMT/NMM/TsO- as the coupling reagent.
Figure 21
Figure 21
IR spectrum of native HA (black line) vs. HA–FFPLADDVTP conjugate (red line) and the spectrum of the used peptide (blue line).
Figure 22
Figure 22
MS spectrum of the obtained polysaccharide–H-FFPLADDVTP-OH conjugate.
Figure 23
Figure 23
Comparison of the IR spectra obtained for the materials coated with the conjugate of hyaluronic acid–peptide (HA–KRMVRISRSL) cross-linked with different cross-linking agents. Approach: chemical modification of the coating layer. (A) Modified 0.5% HA and 20% CA; (B) modified 1% HA and 20% CA; (C) modified 2% HA and 5% CA; (D) modified 1% HA and BDDE.
Figure 23
Figure 23
Comparison of the IR spectra obtained for the materials coated with the conjugate of hyaluronic acid–peptide (HA–KRMVRISRSL) cross-linked with different cross-linking agents. Approach: chemical modification of the coating layer. (A) Modified 0.5% HA and 20% CA; (B) modified 1% HA and 20% CA; (C) modified 2% HA and 5% CA; (D) modified 1% HA and BDDE.
Figure 24
Figure 24
Comparison of the IR spectra obtained for the materials coated with mixture of hyaluronic acid H-FFPLADDVTP-OH and cross-linked with different cross-linking agents. Approach: layer-by-layer physical modification. (A) With 0.5% HA, 20 mg of peptide and 20% CA; (B) 1% HA, 20 mg of peptide, and 20% CA; (C) 2% HA, 20 mg of peptide, and 5% CA; (D) 1% HA, 20 mg of peptide, and BDDE.
Figure 24
Figure 24
Comparison of the IR spectra obtained for the materials coated with mixture of hyaluronic acid H-FFPLADDVTP-OH and cross-linked with different cross-linking agents. Approach: layer-by-layer physical modification. (A) With 0.5% HA, 20 mg of peptide and 20% CA; (B) 1% HA, 20 mg of peptide, and 20% CA; (C) 2% HA, 20 mg of peptide, and 5% CA; (D) 1% HA, 20 mg of peptide, and BDDE.
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