Warning: mkdir(): Permission denied in /home/virtual/lib/view_data.php on line 81

Warning: fopen(upload/ip_log/ip_log_2024-12.txt): failed to open stream: No such file or directory in /home/virtual/lib/view_data.php on line 83

Warning: fwrite() expects parameter 1 to be resource, boolean given in /home/virtual/lib/view_data.php on line 84
Effect of pH and storage time on the elution of residual monomers from polymerized composite resins


Your browser does not support the NLM PubReader view.

Go to this page to see a list of supporting browsers.

Effect of pH and storage time on the elution of residual monomers from polymerized composite resins

Article information

Restor Dent Endod. 2004;29(3):249-266
Publication date (electronic) : 2004 May 31
doi : https://doi.org/10.5395/JKACD.2004.29.3.249
Cheol-Min Jeon1, Hyun-Mi Yoo2, Hyuk-Choon Kwon1
1Department of Conservative Dentistry, College of Dentistry, Seoul National University, Korea.
2Department of Conservative Dentistry, The Institute of Oral Health Science, Samsung Medical Center, Sungkyunkwan University, School of Medicine, Korea.
Corresponding author: Hyuk-Choon Kwon. Department of Conservative Dentistry, College of Dentistry, Seoul National University, 28-2 Yeongun-dong, Chongro-gu, Seoul, Korea, 110-749. Tel: 82-2-2647-2882, Fax: 82-2-2647-7528, juhohyun@hanmail.net

Abstract

Objectives

The purpose of this study was to determine whether pH and time has any influence on the degradation behavior of composite restoration by analyzing the leached monomers of dental composites qualitatively and quantitatively after storage in acetate buffer solution as a function of time using high performance liquid chromatography (HPLC) / mass spectrometer.

Materials and Methods

Three commercial composite restorative resin materials (Z-250, Heliomolar and Aeliteflo) with different matrix structure and filler composition were studied. Thirty specimens (7mm diameter×2mm thick) of each material were prepared. The cured materials were stored in acetate buffer solution at different pH (4, 7) for 1, 7 and 45days. As a reference, samples of unpolymerized composite materials of each product were treated with methanol (10 mg/ml). Identification of the various compounds was achieved by comparison of their mass spectra with those of reference compound, with literature data, and by their fragmentation patterns. Data were analysed statistically using ANOVA and Duncan's test.

Results

1. Amounts of leached TEGDMA in Aeliteflo were significantly larger than those of UDMA in Z-250 and Heliomolar at experimental conditions of different storage time and pH variation (p < 0.001).

2. As to comparison of the amounts of leached monomers per sorage time, amounts of leached TEGDMA in Aeliteflo and UDMA in Z-250 and Heliomolar were increased in the pH 4 solution more significantly than in the pH 7 solution after 1day, 7days and 45days, respectively (p < 0.001).

3. In total amounts of all the leached monomers with storage times, the overall amounts of pH 4 extracts were larger than those of pH 7 extracts for all resin groups, but there was no significant difference (p > 0.05).

Keywords: Light cured composite resin; Leaching of residual monomers; pH variation; High performance liquid chromatography (HPLC)

References

1. Antonucci JM, Bowen RL. Dimethacrylates derived from hydroxylbenzoic acid. J Dent Res 1976. 558–15.
2. Asmussen E. Factors affecting the quantity of remaining double bonds in restorative resin polymers. Scand J Dent Res 1982. 90490–496.
3. Antonucci JM, Toth EE. Extent of polymerization of dental resins by differential scanning calorimetry. J Dent Res 1983. 62(2)121–125.
4. Ruyter IE, Oysaed H. Compressive creep of light cure resin based restorative materials. Acta Odontol Scand 1982. 40319–324.
5. Hanks CT, Craig RG, Diehl ML, Pashley DH. Cytotoxity of dental composites and other materials in a new in vitro device. J Oral Pathol 1988. 17396–403.
6. Ferracane JL, Berge HX, Condon JR. In vitro aging of dental composites in water-effect of degree of conversion, filler volume, and filler/matrix coupling. J Biomed Mater Res 1998. 42465–472.
7. Ferracane JL, DeWald JP. A comparison of four modes of evaluating depth of cure of light activated composite. J Dent Res 1987. 66(3)727–730.
8. Ferracane JL, Condon JR. Rate of elution of leachable components from composite. Dent Mater 1990. 6282–287.
9. Inoue K, Hayashi I. Residual monomer (Bis-GMA) of composite resins. J Oral Rehabil 1982. 9493–497.
10. Tanaka K, Taira M, Shintani H, Wakasa K. Residual monomer(TEGDMA and Bis-GMA)of a set visable-light-cured dental composite resin when immersed in water. J Oral Rehabil 1991. 18353–362.
11. Dickens SH, Stansbury JW, Floyd CJ. Effects of chemical composition on cure properties of dental resins. J Dent Res 1999. 781459–1463.
12. Ferracane JL. Elution of leachable components from composites. J Oral Rehabil 1994. 21441–452.
13. Gerzina TM, Hume WR. Effect of Dentin on the release of TEGDMA from resin composite in vitro. J Oral Rehabil 1994. 21463–468.
14. Santerre JP, Shajii L, Leung BW. Relation of dental composite formulations to their degradation and the release of hydrolyzed polymeric-resin-derived product. Crit Rev Oral Biol Med 2001. 12(2)136–151.
15. Van Groeningen G, Arends J. Composite degradation in vivo. Dent Mater 1986. 2225–227.
16. Göpferich A. Mechanism of polymer degradation and erosion. Biomaterials 1996. 17103–114.
17. Wu W, Toth EE, Moffa JF, Ellison JA. Subsurface damage layer of in vivo worn dental composite restorations. J Dent Res 1984. 63(5)675–680.
18. Wu W, Mckinney JE. Influence of chemicals on wear of dental composites. J Dent Res 1982. 61(10)1180–1183.
19. Soderholm KJ, Zigan M, Ragan M, Bergman M. Hydrolytic degradation of dental composites. J Dent Res 1984. 631248–1254.
20. Soderholm KJ. Degradation of glass filler in experimental composites. J Dent Res 1981. 601867–1872.
21. Hanks CT. Cytotoxic Effects of resin components on culture mammalian fibroblasts. J Dent Res 1991. 701450–1455.
22. Nassiri MR, Hanks CT, Cameron MJ, Strawn SE, Craig RG. Application of Flow cytometry to determine the cytotoxicity of urethane dimethacrylate in human cells. J Biomed Mater Res 1994. 28153–158.
23. Cherry BA, Moon PC, Kalini MY. Estrogenic activity of combined admistration of two possible dental resins. J Dent Res 1998. 77(AADR abst)1080.
24. Arenholt-Bindslev D, Breinholt V, Schmalz G, Preiss A. Time-related bisphenol-A content and estrogenic activity in saliva samples collected in relation to placement of fissure sealants. Clin Oral Investig 1999. 3(3)120–125.
25. McKinney JE, Wu W. Chemical softening and wear of dental composites. J Dent Res 1985. 641326–1331.
26. Geddes DA. Acids produced by human dantal plaque metabolism in situ. Caries Res 1975. 998–109.
27. Asmussen E. Softening of Bis-GMA based polymers by ethanol and by organic acids of plaque. Scand J Dent Res 1984. 92257–261.
28. Choi JH. Gigi bunseog gaelon mich eung-yong 1998. 100–165.
29. Lingstrom P, Imfeld T, Birkhed D. Comparison of three different methods for measurement of plaque-pH in humans after consumption of soft bread and potato chips. J Dent Res 1993. 72(5)865–870.
30. Chadwick RG, McCabe JF, Walls AW, Storer R. The effect of storage media upon the surface microhardness and abrasion resistance if three composites. Dent Mater 1990. 6123–128.
31. Larsen IB, Freund M, Munksgaard EC. Change in surface hardness of BIS_GMA/TEGDMA polymer due to enzymatic action. J Dent Res 1992. 71(11)1851–1853.
32. Yap AU, Tan SH, Wee SS, Lee CW. Chemical degradation of composite restoratives. J Oral Rehabil 2001. 281015–1021.
33. Freund M, Munksgaard EC. Enzymatic degradation of Bis-GMA/TEGDMA-polymers causing decreased microhardness and greater wear in vitro. Scand J Dent Res 1990. 98351–356.
34. Jaffer F, Finer Y, Santerre JP. Interaction between resin monomer and commercial composite resins with human saliva derived esterases. Biomaterials 2002. 23(7)1707–1719.
35. Santerre JP, Shajii L. Biodegradation of commercial dental composites by Cholesterol Esterase. J Dent Res 1999. 78(8)1459–1468.
36. Ruyter IE. Physical and chemical aspects related to substances released from polymer materials in an aqueous environment. Advan Dent Res 1995. 9344–349.
37. Ortengren U, Wellendorf H, Karlsson S, Ruyter IE. Water sorption and solubility of dental composite and identification of monomers released in an aqueous environment. J Oral Rehabil 2001. 28(12)1106–1115.
38. Lee SY, Huang HM. Leached components from dental composites in oral simulating fluids and the resultant composite strengths. J Oral Rehabil 1998. 25575–588.
39. Ortengren U, Andersson F. Influence of pH and storage time on the sorption and solubility behaviour of three composite resin materials. J Dent 2001. 2935–41.
40. Braden M, Davy KW. Water absorption characteristics of some unfilled resins. Biomaterials 1986. 7474–475.
41. Muller H, Olsson S, Soderholm KJ. The effect of comonomer composition, silane heating and filler type on aqueous TEGDMA lechability in model resin composites. Eur J Oral Sci 1997. 105362–376.
42. Braden M, Clarke RL. Water absorption characteristics of dental microfine composite filling materials. Biomaterials 1984. 5369–372.
43. Øysaed H, Ruyter IE. Water sorption and filler characteristics of composites for use in posterior teeth. J Dent Res 1986. 651315–1318.
44. Geurtsen W. Substances released from dental resin composites and glass ionomer cements. Eur J Oral Sci 1998. 106687–695.
45. Soderholm KJ. Degradation of grass filler in experimental composites. J Dent Res 1981. 60(11)1867–1875.
46. Göpferich A. Mechanism of polymer degradation and erosion. Biomaterials 1996. 17103–114.
47. Munksgaard EC, Freund M. Enzymatic hydrolysis of(di) methacrylates and their polymers. Scand J Dent Res 1990. 98261–267.
48. Qvist V. Pulp reactions in human teeth to tooth colored filling material. Scand J Dent Res 1975. 8354–66.
49. Geurtsen W, Spahl W, Leyhausen G. Residual monomer/additive release and variability in cytotoxicity of light-curing glass-ionomer cement and compomers. J Dent Res 1998. 772012–2019.
50. Hume WR, Hood AM. Comparing cytotoxicity in vitro between cured and uncured composite resins. J Dent Res 1990. 69943–951.
51. Stanley HR. Compatability of various materials with oral tissues. J Dent Res 1979. 581507–1517.
52. Stanley HR. Pulpal consideration of adhesive material. Oper Dent 1992. Suppl 5151–164.
53. Rathbun MA, Craig RG, Hanks CT. Cytotoxity of a Bis-GMA dental composite before and after leaching in organic solvent. J Biomed Mater Res 1991. 25443–457.

Article information Continued

Copyright © 2004 Korean Academy of Conservative Dentistry
(open-access) :

This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/by-nc/3.0/) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

Figure 1

Figure 1

LC / MS-chromatogram of STD from Aeliteflo (Unpolymerized material)

Figure 2

Figure 2

LC / MS-chromatogram of pH 4 extract from Aeliteflo (Polymerized material)

Figure 3

Figure 3

LC / MS-chromatogram of pH 7 extract from Aeliteflo (Polymerized material)

Figure 4

Figure 4

LC / MS-chromatogram of STD from Z-250 (Unpolymerized material)

Figure 5

Figure 5

LC / MS-chromatogram of pH 4 extract from Z-250 (Polymerized material)

Figure 6

Figure 6

LC / MS-chromatogram of pH 7 extract from Z-250 (Polymerized material)

Figure 7

Figure 7

LC / MS-chromatogram of STD from Heliomolar (Unpolymerized material)

Figure 8

Figure 8

LC / MS-chromatogram of pH 4 extract from Heliomolar (Polymerized material)

Figure 9

Figure 9

LC / MS - chromatogram of pH 7 extract from Heliomolar (Polymerized material)

Peak A ; Internal caffeine standard, fragmented methyl methacrylate, methacrylic acid, etc.

Peak B ; TEGDMA (triethyleneglycol dimethacrylate)

Peak C ; UDMA (urethane dimethacrylate)

Peak D ; Bis-GMA (Bisphenol A diglycidyl ether dimethacrylate)

Peak E ; Unidentified, probably related to Bis-EMA (Ethoxylated bisphenol A dimethacrylate)

Peak F,G ; A certain dimer or oligomer

Figure 10

Figure 10

MS spectra of Caffeine (9min)

Figure 11

Figure 11

MS spectra of TEGDMA (14min)

Figure 12

Figure 12

MS spectra of UDMA (21min)

Figure 13

Figure 13

MS spectra of Bis-GMA (23min)

Figure 14

Figure 14

Leached TEGDMA of Aeliteflo

Figure 15

Figure 15

Leached UDMA of Z-250

Figure 16

Figure 16

Leached UDMA of Heliomolar

Figure 17

Figure 17

Total amount of leached monomers according to storage time

Table 1

Commercial light-cured dental composite resins used in this study.

Table 1

Bis-GMA = Bisphenol A diglycidyl ether dimethacrylate

TEGDMA = Triethyleneglycol dimethacrylate

Bis-EMA = Etoxylated Bisphenol A dimethacrylate

Bis-EMA (6) = Bisphenol A polyetheylene glycol diether dimethacrylate

UEDMA = Urethane dimethacrylate

D3MA = Decamethacrylate

Table 2

Experimental conditions according to different pH and storage time.

Table 2

Table 3

Dilution of standard solution (STD) and storage solution

Table 3

*ppm = mg/L

Table 4

Conditions of HPLC

Table 4

Table 5

Isolated monomers released at its specific retention time.

Table 5

*Bis-EMA (6) ; Bisphenol A polyetheylene glycol diether dimethacrylate.

Table 6

Chemical structure of fragmented ions related to TEGDMA

Table 6

Table 7

Chemical structure of fragmented ions related to UDMA

Table 7

Table 8

Leached monomer content of Aelitflo groups

Table 8

*%CF = percentage related to the internal caffeine standard

*STD = standard solution (unpolymerized material)

Table 9

Leached monomer content of Z-250 groups

Table 9

Table 10

Leached monomer content of Heliomolar groups

Table 10

Table 11

Amount of leached TEGDMA and UDMA according to storage time (%CF), n = 15

Table 11

*: significantly different on the horizontal line (p < 0.001)

▸values with the same subscript letter in the same row are not significantly different (p > 0.05)

Table 12

Relative percentage of cumulative monomers following 45days storage as to original concentration

Table 12

▾%CF = percentage related to the internal caffeine standard

*%Sol = percentage related to original concentration of STD