pKa value and buffering capacity of acidic monomers commonly used in self-etching primers

Ulrich Salz, Angela Mücke, Jörg Zimmermann, Franklin Chi Meng Tay, David Henry Pashley

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

Purpose: The aim of this investigation was to characterize acidic monomers used in self-etching primers/adhesives by determination of their pKa values and by calculation of their calcium dissolving capacity in comparison with phosphoric and hydrochloric acid. Materials and Methods: The following acidic monomers were included in this study: 4-methacryloyloxyethyl trimellitate anhydride (4-META), 10-methacryloyloxydecyl dihydrogen phosphate (MDP), dimethacryloyloxyethyl hydrogen phosphate (di-HEMA-phosphate), ethyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (EAEPA), 2-[4- (dihydroxyphosphoryl)-2-oxabutyl]acrylic acid (HAEPA), and 2,4,6 trimethylphenyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (MAEPA). The pKa values were obtained by titration with 0.1 mol/I NaOH in aqueous solution. The inflection points of the resulting potentiometric titration curve were determined as pKa values. In the case of the sparingly water-soluble acidic monomers MAEPA and 4-META, the co-solvent method using different water/ethanol ratios for MAEPA or water/acetone ratios for 4-META was used. The dissolving capacity of each acidic monomer is defined as the amount of hydroxyapatite (HA) dissolved by 1 g of acid. For each monomer, the HA dissolving capacity was calculated by the corresponding pKa value and the molecular weight. To confirm the calculated dissolving capacities, increasing amounts of HA powder (100 mg portions) were slowly added to 15 mmol/l aqueous solutions of the monomers to determine how much HA could be dissolved in the acidic solutions. Results: For all the investigated acidic monomers, pKa1 values between 1.7 to 2.5 were observed. The pKa2 values for the phosphate/phosphonate derivatives are between 7.0 and 7.3, and are comparable to phosphoric acid. For dicarboxylic acid derivatives, the pKa2 values are in the range of 4.2 to 4.5. Due to their comparable molecular weights and pKa1 values, the three tested acids di-HEMA phosphate, MDP and 4-META all possess comparable dissolving capacities for HA (ie, 0.26 to 0.28 g/g monomer). The same amount by weight of acidic monomer EAEPA dissolved more HA (ie, 0.35 g/g monomer). Due to their different molecular weights, phosphoric acid and hydrochloric acid dissolved three and ten times as much HA, respectively, as the first three acidic monomers. As a result, the ability of these acids to dissolve HA increases as their molecular weight decreases. Conclusion: There are no significant differences among the investigated acidic monomers in terms of their pKa values and HA dissolving capacities. Monomer selection criteria for new self-etching adhesives must include properties such as calcium salt stability, wetting of the substrate, and copolymerization behavior.

Original languageEnglish (US)
Pages (from-to)143-150
Number of pages8
JournalJournal of Adhesive Dentistry
Volume8
Issue number3
StatePublished - Jul 13 2006

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Durapatite
Anhydrides
Molecular Weight
Adhesives
Acids
Water
Phosphates
Calcium
Organophosphonates
Dicarboxylic Acids
Hydrochloric Acid
Acetone
Powders
Patient Selection
Hydrogen
Ethanol
Salts
Weights and Measures

Keywords

  • 4-META
  • Acid etching
  • Acidic monomer
  • Adhesive
  • Buffering
  • Dentin bonding
  • MDP
  • Self-etching
  • pH value
  • pKa value

ASJC Scopus subject areas

  • Orthodontics
  • Oral Surgery
  • Periodontics

Cite this

pKa value and buffering capacity of acidic monomers commonly used in self-etching primers. / Salz, Ulrich; Mücke, Angela; Zimmermann, Jörg; Tay, Franklin Chi Meng; Pashley, David Henry.

In: Journal of Adhesive Dentistry, Vol. 8, No. 3, 13.07.2006, p. 143-150.

Research output: Contribution to journalArticle

Salz, U, Mücke, A, Zimmermann, J, Tay, FCM & Pashley, DH 2006, 'pKa value and buffering capacity of acidic monomers commonly used in self-etching primers', Journal of Adhesive Dentistry, vol. 8, no. 3, pp. 143-150.
Salz, Ulrich ; Mücke, Angela ; Zimmermann, Jörg ; Tay, Franklin Chi Meng ; Pashley, David Henry. / pKa value and buffering capacity of acidic monomers commonly used in self-etching primers. In: Journal of Adhesive Dentistry. 2006 ; Vol. 8, No. 3. pp. 143-150.
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abstract = "Purpose: The aim of this investigation was to characterize acidic monomers used in self-etching primers/adhesives by determination of their pKa values and by calculation of their calcium dissolving capacity in comparison with phosphoric and hydrochloric acid. Materials and Methods: The following acidic monomers were included in this study: 4-methacryloyloxyethyl trimellitate anhydride (4-META), 10-methacryloyloxydecyl dihydrogen phosphate (MDP), dimethacryloyloxyethyl hydrogen phosphate (di-HEMA-phosphate), ethyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (EAEPA), 2-[4- (dihydroxyphosphoryl)-2-oxabutyl]acrylic acid (HAEPA), and 2,4,6 trimethylphenyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (MAEPA). The pKa values were obtained by titration with 0.1 mol/I NaOH in aqueous solution. The inflection points of the resulting potentiometric titration curve were determined as pKa values. In the case of the sparingly water-soluble acidic monomers MAEPA and 4-META, the co-solvent method using different water/ethanol ratios for MAEPA or water/acetone ratios for 4-META was used. The dissolving capacity of each acidic monomer is defined as the amount of hydroxyapatite (HA) dissolved by 1 g of acid. For each monomer, the HA dissolving capacity was calculated by the corresponding pKa value and the molecular weight. To confirm the calculated dissolving capacities, increasing amounts of HA powder (100 mg portions) were slowly added to 15 mmol/l aqueous solutions of the monomers to determine how much HA could be dissolved in the acidic solutions. Results: For all the investigated acidic monomers, pKa1 values between 1.7 to 2.5 were observed. The pKa2 values for the phosphate/phosphonate derivatives are between 7.0 and 7.3, and are comparable to phosphoric acid. For dicarboxylic acid derivatives, the pKa2 values are in the range of 4.2 to 4.5. Due to their comparable molecular weights and pKa1 values, the three tested acids di-HEMA phosphate, MDP and 4-META all possess comparable dissolving capacities for HA (ie, 0.26 to 0.28 g/g monomer). The same amount by weight of acidic monomer EAEPA dissolved more HA (ie, 0.35 g/g monomer). Due to their different molecular weights, phosphoric acid and hydrochloric acid dissolved three and ten times as much HA, respectively, as the first three acidic monomers. As a result, the ability of these acids to dissolve HA increases as their molecular weight decreases. Conclusion: There are no significant differences among the investigated acidic monomers in terms of their pKa values and HA dissolving capacities. Monomer selection criteria for new self-etching adhesives must include properties such as calcium salt stability, wetting of the substrate, and copolymerization behavior.",
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author = "Ulrich Salz and Angela M{\"u}cke and J{\"o}rg Zimmermann and Tay, {Franklin Chi Meng} and Pashley, {David Henry}",
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TY - JOUR

T1 - pKa value and buffering capacity of acidic monomers commonly used in self-etching primers

AU - Salz, Ulrich

AU - Mücke, Angela

AU - Zimmermann, Jörg

AU - Tay, Franklin Chi Meng

AU - Pashley, David Henry

PY - 2006/7/13

Y1 - 2006/7/13

N2 - Purpose: The aim of this investigation was to characterize acidic monomers used in self-etching primers/adhesives by determination of their pKa values and by calculation of their calcium dissolving capacity in comparison with phosphoric and hydrochloric acid. Materials and Methods: The following acidic monomers were included in this study: 4-methacryloyloxyethyl trimellitate anhydride (4-META), 10-methacryloyloxydecyl dihydrogen phosphate (MDP), dimethacryloyloxyethyl hydrogen phosphate (di-HEMA-phosphate), ethyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (EAEPA), 2-[4- (dihydroxyphosphoryl)-2-oxabutyl]acrylic acid (HAEPA), and 2,4,6 trimethylphenyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (MAEPA). The pKa values were obtained by titration with 0.1 mol/I NaOH in aqueous solution. The inflection points of the resulting potentiometric titration curve were determined as pKa values. In the case of the sparingly water-soluble acidic monomers MAEPA and 4-META, the co-solvent method using different water/ethanol ratios for MAEPA or water/acetone ratios for 4-META was used. The dissolving capacity of each acidic monomer is defined as the amount of hydroxyapatite (HA) dissolved by 1 g of acid. For each monomer, the HA dissolving capacity was calculated by the corresponding pKa value and the molecular weight. To confirm the calculated dissolving capacities, increasing amounts of HA powder (100 mg portions) were slowly added to 15 mmol/l aqueous solutions of the monomers to determine how much HA could be dissolved in the acidic solutions. Results: For all the investigated acidic monomers, pKa1 values between 1.7 to 2.5 were observed. The pKa2 values for the phosphate/phosphonate derivatives are between 7.0 and 7.3, and are comparable to phosphoric acid. For dicarboxylic acid derivatives, the pKa2 values are in the range of 4.2 to 4.5. Due to their comparable molecular weights and pKa1 values, the three tested acids di-HEMA phosphate, MDP and 4-META all possess comparable dissolving capacities for HA (ie, 0.26 to 0.28 g/g monomer). The same amount by weight of acidic monomer EAEPA dissolved more HA (ie, 0.35 g/g monomer). Due to their different molecular weights, phosphoric acid and hydrochloric acid dissolved three and ten times as much HA, respectively, as the first three acidic monomers. As a result, the ability of these acids to dissolve HA increases as their molecular weight decreases. Conclusion: There are no significant differences among the investigated acidic monomers in terms of their pKa values and HA dissolving capacities. Monomer selection criteria for new self-etching adhesives must include properties such as calcium salt stability, wetting of the substrate, and copolymerization behavior.

AB - Purpose: The aim of this investigation was to characterize acidic monomers used in self-etching primers/adhesives by determination of their pKa values and by calculation of their calcium dissolving capacity in comparison with phosphoric and hydrochloric acid. Materials and Methods: The following acidic monomers were included in this study: 4-methacryloyloxyethyl trimellitate anhydride (4-META), 10-methacryloyloxydecyl dihydrogen phosphate (MDP), dimethacryloyloxyethyl hydrogen phosphate (di-HEMA-phosphate), ethyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (EAEPA), 2-[4- (dihydroxyphosphoryl)-2-oxabutyl]acrylic acid (HAEPA), and 2,4,6 trimethylphenyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate (MAEPA). The pKa values were obtained by titration with 0.1 mol/I NaOH in aqueous solution. The inflection points of the resulting potentiometric titration curve were determined as pKa values. In the case of the sparingly water-soluble acidic monomers MAEPA and 4-META, the co-solvent method using different water/ethanol ratios for MAEPA or water/acetone ratios for 4-META was used. The dissolving capacity of each acidic monomer is defined as the amount of hydroxyapatite (HA) dissolved by 1 g of acid. For each monomer, the HA dissolving capacity was calculated by the corresponding pKa value and the molecular weight. To confirm the calculated dissolving capacities, increasing amounts of HA powder (100 mg portions) were slowly added to 15 mmol/l aqueous solutions of the monomers to determine how much HA could be dissolved in the acidic solutions. Results: For all the investigated acidic monomers, pKa1 values between 1.7 to 2.5 were observed. The pKa2 values for the phosphate/phosphonate derivatives are between 7.0 and 7.3, and are comparable to phosphoric acid. For dicarboxylic acid derivatives, the pKa2 values are in the range of 4.2 to 4.5. Due to their comparable molecular weights and pKa1 values, the three tested acids di-HEMA phosphate, MDP and 4-META all possess comparable dissolving capacities for HA (ie, 0.26 to 0.28 g/g monomer). The same amount by weight of acidic monomer EAEPA dissolved more HA (ie, 0.35 g/g monomer). Due to their different molecular weights, phosphoric acid and hydrochloric acid dissolved three and ten times as much HA, respectively, as the first three acidic monomers. As a result, the ability of these acids to dissolve HA increases as their molecular weight decreases. Conclusion: There are no significant differences among the investigated acidic monomers in terms of their pKa values and HA dissolving capacities. Monomer selection criteria for new self-etching adhesives must include properties such as calcium salt stability, wetting of the substrate, and copolymerization behavior.

KW - 4-META

KW - Acid etching

KW - Acidic monomer

KW - Adhesive

KW - Buffering

KW - Dentin bonding

KW - MDP

KW - Self-etching

KW - pH value

KW - pKa value

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M3 - Article

C2 - 16830660

AN - SCOPUS:33745748591

VL - 8

SP - 143

EP - 150

JO - The journal of adhesive dentistry

JF - The journal of adhesive dentistry

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