Next Article in Journal
An Efficient Direction of Arrival Estimation Algorithm for Sources with Intersecting Signature in the Time–Frequency Domain
Previous Article in Journal
Mitigation against DDoS Attacks on an IoT-Based Production Line Using Machine Learning
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Applied Sciences
Volume 11
Issue 4
10.3390/app11041848
applsci-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Calcium Release from Different Toothpastes after the Incorporation of Tricalcium Phosphate and Amorphous Calcium Phosphate

by
Ping-Jen Hou
1,2,
Chang-Yu Lee
3,†,
Keng-Liang Ou
2,4,5,6,7,
Wen-Chien Lan
4,
Yen-Chun Chuo
2,8,
Hung-Yang Lin
9,
Hsiao-Wei Chao
10,
Bai-Hung Huang
2,11,12,
Takashi Saito
6,
Hsin-Yu Tsai
6,
Tzu-Sen Yang
2,13,*,
Christopher J. Walinski
14 and
Muhammad Ruslin
15
1
Graduate Institute of Biomedical Materials and Tissue Engineering, College of Biomedical Engineering, Taipei Medical University, Taipei 110, Taiwan
2
Biomedical Technology R & D Center, China Medical University Hospital, Taichung 404, Taiwan
3
Division of Periodotics, Department of Dentistry, Taipei Medical University Hospital, Taipei 110, Taiwan
4
Department of Oral Hygiene Care, Ching Kuo Institute of Management and Health, Keelung 203, Taiwan
5
Department of Dentistry, Taipei Medical University-Shuang Ho Hospital, New Taipei City 235, Taiwan
6
Division of Clinical Cariology and Endodontology, Department of Oral Rehabilitation, School of Dentistry, Health Sciences University of Hokkaido, Hokkaido 061-0293, Japan
7
3D Global Biotech Inc. (Spin-off Company from Taipei Medical University), New Taipei City 221, Taiwan
8
School of Dental Technology, College of Oral Medicine, Taipei Medical University, Taipei 110, Taiwan
9
Department of Dentistry, Fu Jen Catholic University Hospital, Fu Jen Catholic University, New Taipei City 243, Taiwan
10
Department of Dentistry, University of Debrecen, 4032 Debrecen, Hungary
11
Implant Academy of Minimally Invasive Dentistry, Taipei 106, Taiwan
12
Asia Pacific Laser Institute, New Taipei City 220, Taiwan
13
Graduate Institute of Biomedical Optomechatronics, College of Biomedical Engineering, Taipei Medical University, Taipei 110, Taiwan
14
Department of Dental Medicine, Touro College of Dental Medicine, Hawthorne, New York, NY 10532, USA
15
Department of Oral and Maxillofacial Surgery, Faculty of Dentistry, Hasanuddin University, Makassar 90245, Indonesia
 
add Show full affiliation list
 
remove Hide full affiliation list
*
Author to whom correspondence should be addressed.
†
This author contributed as co-first author to this paper.
Appl. Sci. 2021, 11(4), 1848; https://doi.org/10.3390/app11041848
Submission received: 14 January 2021 / Revised: 9 February 2021 / Accepted: 15 February 2021 / Published: 19 February 2021
(This article belongs to the Section Materials Science and Engineering)
Browse Figures
Versions Notes

Abstract

:
This study aimed to investigate the free calcium released from different brands of toothpaste after incorporation with a beta-tricalcium phosphate (β-TCP)/amorphous calcium phosphate (ACP) mixed powder and with β-TCP powder alone. Four brands of toothpaste were used for the experiment: Nano-Bio Activation Toothpaste, Colgate Total Advanced Whitening Toothpaste, BORONIA Herbal Whitening, and BioMin F. The investigated β-TCP and ACP powders were prepared by a two-step sintering method using raw coral material. Analytical results found that the mean calcium concentration of the β-TCP/ACP (2:1) powder in deionized water was 3.4% when the pH was between 5 and 9. Moreover, statistical results revealed that the toothpaste containing β-TCP powder had significantly higher calcium concentrations than the normal toothpaste. The toothpaste containing mixed β-TCP/ACP powder had a higher calcium concentration than the toothpaste containing only β-TCP powder. Twice as much free calcium could be released from β-TCP/ACP toothpaste than from β-TCP-only toothpaste. Thus, toothpaste containing β-TCP/ACP mixed powder offers greater benefits to facilitate the remineralization of enamel than toothpaste containing only β-TCP.

1. Introduction

The human oral environment undergoes a dynamic process of demineralization and remineralization every day. The oral environment changes from neutral to acidic due to metabolites produced by bacteria in the mouth. An acidic oral environment causes demineralization of the tooth surface, leading to caries, periodontal disease, and tooth sensitivity. In the demineralization process, calcium phosphate (CaP) crystals on the surface of teeth are dissolved by the acidic environment, causing a loss of calcium ions. However, the oral environment can be made to return to neutral by performing oral cleaning, thus halting tooth surface demineralization. Subsequently, the free calcium and phosphate in the saliva will re-enter the tooth surface to form a protective layer of CaP crystals in a remineralization process [1,2,3]. Therefore, calcium ions are a crucial element of the oral environment since their presence can promote the formation of CaP crystals inside the teeth during the remineralization process.
It is well known that the outer enamel of human teeth consists of micron-sized calcium carbonate (CaCO3) deficient hydroxyapatite (HAP) microcrystals [4]. The main component of the outer enamel is HAP (around 97%) [5,6]. Recent studies have found that CaP, such as amorphous calcium phosphate (ACP), beta-tricalcium phosphate (β-TCP), and alpha-tricalcium phosphate (α-TCP), are similar to the natural enamel [7,8,9]. Among all compounds of CaP crystals, β-TCP and ACP are the most commonly used in oral care applications [10,11]. Although most CaP additives need to release calcium ions under acidic conditions, β-TCP can provide the best calcium ion release effect even in a neutral pH environment [12]. Accordingly, β-TCP is regarded as a stable tricalcium phosphate at room temperature. Hemagaran et.al. [12] also demonstrated that using β-TCP can increase calcium levels in saliva and promote the remineralization of tooth surface. In addition, it was also found that ACP presented as a unique artificial HAP [4]. Previously published studies have shown that ACP has good bone conduction and biodegradability, enhances cell proliferation ability, and promotes cell adhesion [13,14]. Moreover, ACP and its composites are considered to be an effective remineralization agent that is often used for remineralization in the dental fields [15,16,17,18].
As stated above, an adequate increase in the amount of free calcium and phosphate in the oral environment plays an important role in facilitating tooth surface remineralization during oral cleaning. From an oral care point of view, it would be beneficial if daily use toothpastes could be developed with the addition of various remineralization agents to prevent the formation of caries without sacrificing any useful properties. Hence, the present study reports on the synthesis and characterization of β-TCP and ACP derived from coral-based raw material through a two-stage sintering method. We aimed to investigate the concentration of calcium in toothpaste incorporated with β-TCP and ACP powders. We hypothesized that adding β-TCP and ACP to toothpaste would increase the release of free calcium in the oral environment, which might be potentially beneficial for the tooth remineralization process.

2. Materials and Methods

2.1. Sample Sintering

The raw coral materials were provided by Popeye Marine Biotechnology Limited (New Taipei City, Taiwan). A two-step sintering method was performed using a heating furnace. For the TCP powder, specimens were first heated for 1 h with a 3 °C/min ramp rate to 800 °C, then heated again to higher temperatures (1100 and 1200 °C). Afterwards, specimens were soaked with a 5 °C/min ramp rate for 1, 2, and 3 h, respectively. For the ACP powder, the specimens were obtained through the precipitation method. In the first sintering process, the specimens were maintained at 700 °C; afterward, the specimens were continually heated at higher temperatures above 800 and 900 °C. Finally, the specimens were soaked with a 5 °C/min ramp rate for 1 h.

2.2. Characteristics of the Sintered TCP and ACP Powders

Powder X-ray diffractometry (XRD; Model 2200, Rigaku Co., Tokyo, Japan) was used to identify the crystallinity of the untreated TCP and ACP. For excitation, monochromatic Cu Kα radiation was generated, operating at 40 kV and 30 mA. The XRD data were taken over a 2θ range of 20°–45° at the account time of 5 s and a step size of 0.04°/step. All of the corresponding peaks were analyzed according to the database from the Joint Committee on Powder Diffraction Standards (JCPDS). The different numbers of peaks represent the characteristic peaks of different samples. The Fourier-transform infrared (FTIR) spectra of sintered TCP and ACP powders were obtained in diffuse reflection mode through the potassium bromide pellet method. The FTIR spectra obtained were in the range of from 400 to 4000 cm−1 (Perkin Elmer Inc., Waltham, MA, USA). An NR-1800 Raman spectrophotometer (JASCO, Tokyo, Japan) was used to measure the Raman spectra of sintered TCP and ACP powders using charge-coupled device detector and an exposure time of 4 s.

2.3. Preparation of Samples for pH Measurements

The pH value of the investigated samples was measured by a pH meter (PB-10 pH meter, Sartorius AG, Goettingen, Germany). As much as 1 g of the sample was weighed out into a 100 mL beaker, deionized water was added to the mark, and then the sample was dispersed for 1 h by using a magnetic plate. The pH meter was then calibrated and inserted into the beaker. Finally, the pH meter readings were recorded.

2.4. Preparation of TCP/ACP Powders Mixed Toothpaste

The TCP powders calcined at 1100 °C for 1 h were mixed in a 2:1 ratio with the ACP powder calcined at 900 °C for 1 h. Afterward, the mixed powder was added to each gram of toothpaste in ratios of 10% and 25%, and then, the mixture was stirred evenly for testing. Four brands of toothpaste were used in this study: Nano-Bio Activation Toothpaste (Pac-Dent Inc., Brea, CA, USA), Colgate Total Advanced Whitening Toothpaste (Colgate-Palmolive Company, New York, NY, USA), Boronia Herbal Whitening (BORONIA, Taichung, Taiwan), and BioMin F toothpaste (BioMin Technologies Limited, London, UK). The ingredients of the investigated toothpastes are listed in Table 1. The effect of free calcium released after the TCP and TCP/ACP powders were incorporated with the toothpastes was then evaluated.

2.5. Measurement of Calcium Release

The calcium concentration of each sample was measured by ethylenediaminetetraacetic acid (EDTA, Sigma Aldrich, Taipei, Taiwan) titration. At first, as much as 1 g of the mixed powder or 2 g of the powder mixed with toothpaste was weighed out accurately using an Erlenmeyer flask; then, deionized water was added, and the mixture was stirred for about 1 h on a magnetic plate until it was well-dispersed. Afterwards, the sample was centrifuged for about 30 min until a clear supernatant was obtained. Following this procedure, 10 mL of the supernatant was pipetted into a 250 mL of Erlenmeyer flask. Then, 20 mL of deionized water and 20 mL of NH3·H2O-NH4Cl buffer solution were added to bring the pH to 10.0. After the solution was mixed well, 2 drops of Eriochrome Black T indicator (Sigma Aldrich, Taipei, Taiwan) were added, and the flask was swirled. Finally, 0.01 M EDTA was titrated to the blue endpoint, at which point the volume recorded was equal to the difference between the final endpoint and the starting point, measured in mL.

2.6. Statistical Analysis

SPSS 19.0 software (SPSS Inc., Chicago, IL, USA) was used to conduct the statistical analysis. In order to compare the calcium concentration between different brands of toothpaste, an ANOVA test was conducted. The value obtained was considered statistically significant with a p-value < 0.05.

3. Results

3.1. XRD Analysis of the Untreated TCP and ACP Samples

Figure 1a shows the XRD patterns of the untreated TCP. We observed that the raw material resembled the structure of CaP closely, indicating that TCP accounted for most of the TCP/HAP biphasic coral powder. According to the (0210) plane in the XRD pattern, the TCP sample can be identified as β-TCP. In addition, based on JCPDS card 00-009-0169, the result was a typical tricalcium phosphate structure, and its quality was indexed. Furthermore, no additional diffraction peaks were found, indicating that the untreated TCP had a single tricalcium phosphate structure. Figure 1b shows the XRD patterns of the untreated ACP. The results show a broadband of ACP presence in the XRD pattern. Moreover, a weak peak of Ca10(PO4)6(OH)2 was also found, with the characteristic peak of the (211) plane as a reference.

3.2. FTIR Analysis of the Sintered TCP and ACP Samples

Figure 2 highlights the effect of different heat treatment temperatures and heat treatment times on the sample structure. FTIR spectra were used to test the TCP calcined at 1100 °C for 1, 2, and 3 h, the TCP calcined at 1200 °C for 2 h, and the ACP calcined at 800 and 900 °C for 1 h. It was found that the two bands at 1030 and 560 cm−1 could be assigned to the stretching (P–O) and the deformation (O–P–O) vibration modes of PO43−, respectively. The raw materials of both the TCP and the ACP showed broad peaks with a less resolved feature for the ACP. The characteristic peak of PO43− at 1100 cm−1 was enhanced significantly after sintering, which indicates that the structure of the ACP was changed to α-TCP and β-TCP at 800 and 900 °C. After the heat treatment, some fine peaks were resolved in the TCP and ACP spectra, suggesting an increase in molecular movement. The appearance of the TCP 1200 °C/2 h became similar to that of the intact TCP. Moreover, the fine peak positions (630, 600, and 570 cm−1) for the deformation vibration mode were found to be almost the same for the both the heated TCP and the ACP, while those for the stretching vibration mode looked different. A very sharp peak at 1138 cm−1 was found only in the 1100 °C-heated TCP spectra.

3.3. Raman Analysis of the Sintered TCP and ACP Samples

Figure 3a,b display the Raman spectra of the sintered TCP and ACP samples. The characteristic peaks at 960 cm−1, which were assigned to the symmetric stretching mode of PO43−, appeared in both the TCP and the ACP samples after sintering. In addition, when the treatment temperature (TCP 1 h, ACP 2 h) or the heat treatment time was increased (for TCP 1100 °C), the peak shifted to a higher wavenumber (ν) and the bandwidth at its half-height (W1/2) became smaller. This finding indicated that compressive stress was imparted to the PO43− moiety due to some internal compaction, and crystallinity increased (Figure 3c,d).

3.4. Comparison of Calcium Concentration at Various pH

Figure 4 illustrates the free calcium concentration of 1 g of TCP/ACP mixed powder at different pH levels. It was observed that the TCP/ACP mixed powder showed a stable amount of free calcium release with an average concentration of 3.4% in the pH 5 to pH 9 range. This range meets the pH requirements for manufacturing a toothpaste. In addition, the calcium concentration increased significantly to 5.0 and 6.2 at pH 10 and pH 11. Although a higher free calcium release was noticed at pH 10 and 11, we assume that it may have been caused by the calcium oxide remaining from the incomplete sintering process of some of the raw material.

3.5. Comparison of Calcium Concentration of Normal Toothpastes

Figure 5a depicts the free calcium concentration of different brands of toothpaste containing TCP powder. It was found that the mean calcium concentrations for 1 g of each toothpaste without TCP powder was 0, 0, 0.10, and 0.11, respectively. The mean calcium concentration obtained from 1 g of each toothpaste containing the 10 wt% TCP powder was 1.38 ± 0.10, 1.56 ± 0.21, 1.26 ± 0, and 1.69 ± 0.21, respectively. In addition, the mean calcium concentration of 1 g of toothpaste containing the 25 wt% TCP powder was 2.14 ± 0.07, 2.39, 1.69 ± 0.17, and 1.69 ± 0.17, respectively. The toothpaste containing TCP powder had a significantly higher calcium concentration than normal toothpaste.
Figure 5b shows the free calcium concentration of different brands of toothpaste containing the TCP/ACP mixed powder. The mean calcium concentration for 1 g of each normal toothpaste was 0, 0, 0.1, and 0.11, respectively. The mean calcium concentration obtained from 1 g of each toothpaste containing the 10 wt% TCP/ACP mixed powder was 1.8, 1.8, 1.8, and 1.8, respectively. Moreover, each 1 g of toothpaste containing the 25 wt% TCP/ACP mixed powder had a mean calcium concentration of 2.79 ± 0.17, 2.79 ± 0.17, 3.09 ± 0.17, and 2.69 ± 0.30, respectively. The toothpaste containing the TCP/ACP mixed powder had a higher calcium concentration than the toothpaste containing only the TCP powder.\

4. Discussion

In the present study, we prepared TCP and ACP powders from coral-based raw material and added the powders into commercially available toothpaste in concentrations of 10% and 25%. The quantity of free calcium released from the toothpaste was then measured. It was found that the raw material had almost completely changed from a CaCO3 structure to a CaP structure by means of a two-step sintering method. It is known that the raw material made from coral is mainly comprised of CaCO3 and calcium oxide (CaO) and that CaCO3 and CaO are the main chemical compounds supporting the bone and tooth remineralization process [7,19]. Previously published studies indicated that high temperature and high pressure could replace the CaCO3 of coral with HAP or TCP, which is a process known as replamineform [20,21]. In accordance with the previous studies, here, we found that high temperature and high pressure promoted the conversion of HAP to TCP following the previous chemical reaction. We also found that the structure of the ACP was changed to α-TCP and β-TCP at 800 and 900 °C [22,23]. A similar result was also seen in previous studies discovering that ACP could be converted to α-TCP and β-TCP after sintering at 800 and 900 °C [24,25].
We also found that the mixed TCP and ACP powders released a stable amount of free calcium in the pH 5 to pH 9 range. A previous study demonstrated that pH has a significant effect on ACP precipitation during the synthesis process, in which some crystalline CaP forms at pH 8 to pH 9 and ACP forms at pH 10 to pH 11 [23]. The oral environment, on the whole, is composed of saliva and gingival fluid, which are rich with calcium ions, phosphate ions, and fluoride ions. In a neutral pH, these components bring a dynamic equilibrium between the HAP in the teeth and in the oral fluid [26,27]. When the pH decreases to acidic (pH below 5.5), the oral environment becomes undersaturated, causing HAP crystals to release from the teeth into the oral biofilm, resulting in mineral dissolution. In conditions where the pH increases to over 4.5, the increased release of PO43− and Ca2+ ions causes supersaturation in the oral fluid. This process leads to the precipitation of the minerals back to the enamel surface [28,29].
Four commercial toothpastes were tested to evaluate the effect of free calcium release after being combined with TCP powder and TCP/ACP powder. We observed that the free calcium concentration increased significantly no matter which brand of toothpaste was combined with the 10% or 25% TCP powder. The concentration of free calcium increased even more in toothpaste containing the mixed TCP/ACP powder. It was previously believed that ACP could be converted to α-TCP and β-TCP through the sintering process [24,25]. Some previously published studies discovered that ACP has a potential role in promoting the HAP assembly into highly-ordered structures [30,31]. High-order HA architectures were detected when the initial nanosphere particles were aggregated, with the structure consisting of ACP shells and HA cores. Similarly, Posner et al. [32] demonstrated that ACP contains a well-defined local structural unit with a compositional constancy covering the broad conditions of preparative solutions, indicating the presence of a core structure. Based on previous findings, we presume that a core–shell structure might have been formed during the sintering process in the present study. As illustrated in Figure 6, the proposed mechanism is one in which the formed core–shell structure contained an inner ACP core coated with an outer TCP shell. The inner ACP core released free calcium at the same time as the outer TCP shell released free calcium. Through this mechanism, the toothpaste containing TCP/ACP powder released a higher concentration of free calcium than the toothpaste containing TCP alone, which could prove beneficial in promoting enamel surface remineralization. However, the possibility of increased formation of calculus should be evaluated due to more free calcium being released into the oral environment. Excess calcium can be retained easily in the oral cavity. Calculus may occur when calcium is deposited gradually [33]. The most direct preventive method would be to add anti-calculus agents to the toothpaste [34]. As long as sufficient anti-calculus agents are included in the toothpaste, the recurrence rate of calculus can be significantly reduced [34,35,36]. Experimentally, the toothpaste containing mixed β-TCP/ACP (2:1) powder is beneficial for the remineralization of enamel, but it can lead to other environmental changes in the oral cavity. These issues need to be further investigated in the future.

5. Conclusions

The present study fully characterized β-TCP and ACP powders fabricated using a two-stage sintering process. The β-TCP/ACP powder mixed in a 2:1 ratio could stably release a free calcium concentration into water with a pH range of 5 to 9. Adding β-TCP/ACP mixed powder to toothpaste could release nearly twice as many free calcium ions than adding β-TCP powder alone. Thus, the high calcium concentration released from toothpastes containing β-TCP/ACP mixed powder might be beneficial as an effective remineralization agent when applied in dental care.

Author Contributions

Writing—original draft, P.-J.H.; investigation, P.-J.H. and C.-Y.L.; data curation, Y.-C.C., H.-Y.L., and H.-W.C.; methodology, B.-H.H. and W.-C.L.; supervision, K.-L.O., C.J.W. and T.S.; validation, H.-Y.T. and M.R.; writing—review and editing, T.-S.Y. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data is contained within the article.

Acknowledgments

The authors would like to thank the Pac-Dent, Inc. for technical support in this paper.

Conflicts of Interest

The authors declare no conflict of interest in this work.

References

  1. Featherstone, J.D. Dental caries: A dynamic disease process. Aust. Dent. J. 2008, 53, 286–291. [Google Scholar] [CrossRef] [PubMed]
  2. Paes Leme, A.F.; Dalcico, R.; Tabchoury, C.P.; Del Bel Cury, A.A.; Rosalen, P.L.; Cury, J.A. In situ effect of frequent sucrose exposure on enamel demineralization and on plaque composition after APF application and F dentifrice use. J. Dent. Res. 2004, 83, 71–75. [Google Scholar] [CrossRef] [PubMed]
  3. Tanaka, M.; Matsunaga, K.; Kadoma, Y. Correlation in inorganic ion concentration between saliva and plaque fluid. J. Med. Dent. Sci. 2000, 47, 55–59. [Google Scholar] [PubMed]
  4. Meyer, F.; Amaechi, B.T.; Fabritius, H.O.; Enax, J. Overview of Calcium Phosphates used in Biomimetic Oral Care. Open Dent. J. 2018, 12, 406–423. [Google Scholar] [CrossRef] [PubMed]
  5. Enax, J.; Epple, M. Synthetic hydroxyapatite as a biomimetic oral care agent. Oral Health Prev. Dent. 2018, 16, 7–19. [Google Scholar] [PubMed]
  6. Dorozhkin, S.V.; Epple, M. Biological and medical significance of calcium phosphates. Angew. Chem. Int. Ed. Engl. 2002, 41, 3130–3146. [Google Scholar] [CrossRef]
  7. Al-Maula, B.H. Calcium oxide nanoparticles effect on the initial caries remineralization. Aip Conf. Proc. 2020, 2213, 020120. [Google Scholar]
  8. Van Loveren, C. (Ed.) Toothpastes: Monographs in Oral Science; Karger: Basel, Switzerland, 2013; Volume 23. [Google Scholar]
  9. Amaechi, B.T.; van Loveren, C. Fluorides and non-fluoride remineralization systems. Monogr. Oral. Sci. 2013, 23, 15–26. [Google Scholar]
  10. Lata, S.; Varghese, N.; Varughese, J.M. Remineralization potential of fluoride and amorphous calcium phosphate-casein phospho peptide on enamel lesions: An in vitro comparative evaluation. J. Conserv. Dent. JCD 2010, 13, 42. [Google Scholar] [CrossRef] [Green Version]
  11. Walsh, L. Contemporary technologies for remineralisation therapies: A review. Int. Dent. SA 2009, 11, 6–16. [Google Scholar]
  12. Hemagaran, G.; Neelakantan, P. Remineralization of the tooth structure—The future of dentistry. Int. J. Pharmtech. Res. 2014, 6, 487–493. [Google Scholar]
  13. Li, Y.B.; Li, D.X.; Weng, W.J. Amorphous calcium phosphates and its biomedical application. J. Inorgan. Mater. 2007, 22, 775–782. [Google Scholar]
  14. Sun, W.; Zhang, F.; Guo, J.; Wu, J.; Wu, W. Effects of Amorphous Calcium Phosphate on Periodontal Ligament Cell Adhesion and Proliferation in vitro. J. Med. Biol. Eng. 2008, 28, 31–37. [Google Scholar]
  15. Zhao, J.; Liu, Y.; Sun, W.B.; Zhang, H. Amorphous calcium phosphate and its application in dentistry. Chem. Cent. J. 2011, 5, 40. [Google Scholar] [CrossRef] [Green Version]
  16. Xu, H.H.; Moreau, J.L.; Sun, L.; Chow, L.C. Nanocomposite containing amorphous calcium phosphate nanoparticles for caries inhibition. Dent. Mater. 2011, 27, 762–769. [Google Scholar] [CrossRef] [Green Version]
  17. Shetty, N.; Kundabala, M. Biominerals in restorative dentistry. J. Interdiscip. Dent. 2013, 3, 64–70. [Google Scholar] [CrossRef]
  18. Melo, M.A.; Weir, M.D.; Passos, V.F.; Powers, M.; Xu, H.H. Ph-activated nano-amorphous calcium phosphate-based cement to reduce dental enamel demineralization. Artif. Cells Nanomed. Biotechnol. 2017, 45, 1778–1785. [Google Scholar] [CrossRef]
  19. Babu, N.R.; Rao, K.P.; Kumar, T.S.S. Effect of coralline derived biphasic calcium phosphate shot blasting on titanium surfaces. Trans. Indian Inst. Met. 2004, 57, 85–89. [Google Scholar]
  20. Urist, M.R.; O’Connor, B.T. Bone Graft, Derivatives and Substitutes; Butterworth-Heinemann Ltd.: Boston, MA, USA, 1994. [Google Scholar]
  21. Roy, D.M.; Linnehan, S.K. Hydroxyapatite formed from coral skeletal carbonate by hydrothermal exchange. Nature 1974, 247, 220–222. [Google Scholar] [CrossRef] [PubMed]
  22. Combes, C.; Rey, C. Amorphous calcium phosphates: Synthesis, properties and uses in biomaterials. Acta Biomater. 2010, 6, 3362–3378. [Google Scholar] [CrossRef] [Green Version]
  23. Vecstaudza, J.; Locs, J. Novel preparation route of stable amorphous calcium phosphate nanoparticles with high specific surface area. J. Alloy. Compd. 2017, 700, 215–222. [Google Scholar] [CrossRef]
  24. Dorozhkin, S.V. Multiphasic calcium orthophosphate (CaPO4) bioceramics and their biomedical applications. Ceram. Int. 2016, 42, 6529–6554. [Google Scholar] [CrossRef]
  25. Zou, C.; Cheng, K.; Weng, W.; Song, C.; Du, P.; Shen, G.; Han, G. Characterization and dissolution–reprecipitation behavior of biphasic tricalcium phosphate powders. J. Alloy. Compd. 2011, 509, 6852–6858. [Google Scholar] [CrossRef]
  26. Leitão, T.J.; Cury, J.A.; Tenuta, L.M.A. Kinetics of calcium binding to dental biofilm bacteria. PLoS ONE 2018, 13, e0191284. [Google Scholar] [CrossRef] [Green Version]
  27. Seredin, P.; Goloshchapov, D.; Prutskij, T.; Ippolitov, Y. Phase Transformations in a Human Tooth Tissue at the Initial Stage of Caries. PLoS ONE 2015, 10, e0124008. [Google Scholar] [CrossRef]
  28. Usha, C.; Sathyanarayanan, R. Dental caries—A complete changeover (Part I). J. Conserv. Dent. 2009, 12, 46–54. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  29. Lijima, M.; Hayashi, K.; Moriwaki, Y. Effects of the Ca2+ and PO43− ion flow on the lengthwise growth of octacalcium phosphate in a model system of enamel crystal formation with controlled ionic diffusion. J. Cryst. Growth 2002, 234, 539–544. [Google Scholar]
  30. Dorozhkin, S.V. Amorphous calcium (ortho)phosphates. Acta Biomater. 2010, 6, 4457–4475. [Google Scholar] [CrossRef] [PubMed]
  31. Tao, J.; Pan, H.; Zeng, Y.; Xu, X.; Tang, R. Roles of amorphous calcium phosphate and biological additives in the assembly of hydroxyapatite nanoparticles. J. Phys. Chem. B 2007, 111, 13410–13418. [Google Scholar] [CrossRef] [PubMed]
  32. Posner, A.S.; Betts, F. Synthetic amorphous calcium phosphate and its relation to bone mineral structure. Acc. Chem. Res. 1975, 8, 273–281. [Google Scholar] [CrossRef]
  33. Jepsen, S.; Deschner, J.; Braun, A.; Schwarz, F.; Eberhard, J. Calculus removal and the prevention of its formation. Periodontol. 2000 2011, 55, 167–188. [Google Scholar] [CrossRef] [PubMed]
  34. Jin, Y.; Yip, H.K. Supragingival calculus: Formation and control. Crit. Rev. Oral Biol. Med. 2002, 13, 426–441. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  35. Mandel, I.D. Calculus update: Prevalence, pathogenicity and prevention. J. Am. Dent. Assoc. 1995, 126, 573–580. [Google Scholar] [CrossRef]
  36. White, D.J. Dental calculus: Recent insights into occurrence, formation, prevention, removal and oral health effects of supragingival and subgingival deposits. Eur. J. Oral. Sci. 1997, 105, 508–522. [Google Scholar] [CrossRef] [PubMed]
Applsci 11 01848 g001a 550Applsci 11 01848 g001b 550
Figure 1. XRD patterns of (a) untreated tricalcium phosphate (TCP) powder and (b) untreated amorphous calcium phosphate (ACP) powder. (a) Peaks corresponding to 0210, 128, and 220 of the TCP (black cube), respectively. The blue star (HAP) is not visible, indicating that most of the raw materials were β-TCP. (b) A broad diffraction peak, which is characteristic of the amorphous state of ACP (blue line). Only one peak corresponding to 211 of the HAP (black cube) exists, indicating that most of the raw materials were ACP. The x-axis of the spectra is the defined diffraction angle between the incident and the reflected x-ray; the y-axis is the extent of the crystallinity of the particular plane.
Figure 1. XRD patterns of (a) untreated tricalcium phosphate (TCP) powder and (b) untreated amorphous calcium phosphate (ACP) powder. (a) Peaks corresponding to 0210, 128, and 220 of the TCP (black cube), respectively. The blue star (HAP) is not visible, indicating that most of the raw materials were β-TCP. (b) A broad diffraction peak, which is characteristic of the amorphous state of ACP (blue line). Only one peak corresponding to 211 of the HAP (black cube) exists, indicating that most of the raw materials were ACP. The x-axis of the spectra is the defined diffraction angle between the incident and the reflected x-ray; the y-axis is the extent of the crystallinity of the particular plane.
Applsci 11 01848 g001aApplsci 11 01848 g001b
Applsci 11 01848 g002 550
Figure 2. FTIR spectra of (a) sintered TCP and (b) sintered ACP powder. The results from (a) show that TCP can be generated stably at a temperature of 1300 °C. The results from (b) indicate that the structure of ACP was converted into TCP after heat treatment. The x-axis of the spectra is the frequency of infrared light, or wave numbers, measured in reciprocal centimeters (cm−1); the y-axis is the infrared light transmittance.
Figure 2. FTIR spectra of (a) sintered TCP and (b) sintered ACP powder. The results from (a) show that TCP can be generated stably at a temperature of 1300 °C. The results from (b) indicate that the structure of ACP was converted into TCP after heat treatment. The x-axis of the spectra is the frequency of infrared light, or wave numbers, measured in reciprocal centimeters (cm−1); the y-axis is the infrared light transmittance.
Applsci 11 01848 g002
Applsci 11 01848 g003 550
Figure 3. Raman spectra (a,b) and crystallinity analysis (c,d) of the sintered TCP and ACP shows that heat treatment not only promoted the formation of TCP and converted ACP into TCP but also increased crystal strength. The x-axis of the Raman spectra is the frequency of light measured in reciprocal centimeters; the y-axis is scattered light.
Figure 3. Raman spectra (a,b) and crystallinity analysis (c,d) of the sintered TCP and ACP shows that heat treatment not only promoted the formation of TCP and converted ACP into TCP but also increased crystal strength. The x-axis of the Raman spectra is the frequency of light measured in reciprocal centimeters; the y-axis is scattered light.
Applsci 11 01848 g003
Applsci 11 01848 g004 550
Figure 4. Free calcium concentration of TCP/ACP mixed powder at different pH values. The TCP/ACP mixed powder showed a stable amount of free calcium release with an average concentration of 3.4% in the pH 5 to pH 9 range.
Figure 4. Free calcium concentration of TCP/ACP mixed powder at different pH values. The TCP/ACP mixed powder showed a stable amount of free calcium release with an average concentration of 3.4% in the pH 5 to pH 9 range.
Applsci 11 01848 g004
Applsci 11 01848 g005a 550Applsci 11 01848 g005b 550
Figure 5. Free calcium concentration of different brands of toothpaste containing (a) TCP powder only and (b) TCP/ACP mixed powder (*** p < 0.001). The toothpaste containing only TCP powder had a significantly higher calcium concentration than the normal toothpaste. Furthermore, the toothpaste containing the TCP/ACP mixed powder had a higher calcium concentration than the toothpaste containing only TCP powder.
Figure 5. Free calcium concentration of different brands of toothpaste containing (a) TCP powder only and (b) TCP/ACP mixed powder (*** p < 0.001). The toothpaste containing only TCP powder had a significantly higher calcium concentration than the normal toothpaste. Furthermore, the toothpaste containing the TCP/ACP mixed powder had a higher calcium concentration than the toothpaste containing only TCP powder.
Applsci 11 01848 g005aApplsci 11 01848 g005b
Applsci 11 01848 g006 550
Figure 6. The proposed mechanism of free calcium release from core–shell-structured ACP.
Figure 6. The proposed mechanism of free calcium release from core–shell-structured ACP.
Applsci 11 01848 g006
Table
Table 1. The ingredients of the investigated toothpastes.
Table 1. The ingredients of the investigated toothpastes.
ProductBrandActive IngredientsInactive Ingredients
iBrite
Nano-Bio Activation Toothpaste		Pac-Dent Inc., USAsodium fluoride, potassium nitratesaccharin sodium, FD&C blue #1, FD&C green #3, glycerin, hydrated silica, polyethylene glycol 400, water, sodium lauryl sulfate, sodium pyrophosphate, sodium citrate, sodium phosphate, tribasic, carboxy methylcellulose sodium
Advanced Whitening ToothpasteColgate-Palmolive Company, USAsodium fluoride, triclosanwater, hydrated silica, glycerin, sorbitol, butyl ester of methyl vinyl ether/maleic anhydride copolymer, sodium lauryl sulfate, sodium hydroxide, propylene glycol, saccharin sodium, carboxy methylcellulose sodium, titanium dioxide, carrageenan
Herbal Whitening ToothpasteBoronia, Taiwansodium mono fluoro phosphatewater, butylene glycol, panax ginseng root extract, vinegar, pruns mume fruit extract, allium sativum (garlic) bulb extract, platycondon grandiflorum root extract, codonopsis lanceolata root extract, rubus fruticcsus (blackberry) fruit extract, acanthopanax senticosus (eleuthero) root extract, glycine soja (soybean) seed extract, oryza sativa (rice) extract, sesamum indicum (sesame) seed extract
BioMin F ToothpasteBioMin Technologies Limited, UKfluoro calcium phospho silicateglycerin, silica, polyethylene glycol 400, sodium lauryl sulphate, titanium dioxide, aroma, carbomer, potassium acesulfame.
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Hou, P.-J.; Lee, C.-Y.; Ou, K.-L.; Lan, W.-C.; Chuo, Y.-C.; Lin, H.-Y.; Chao, H.-W.; Huang, B.-H.; Saito, T.; Tsai, H.-Y.; et al. Calcium Release from Different Toothpastes after the Incorporation of Tricalcium Phosphate and Amorphous Calcium Phosphate. Appl. Sci. 2021, 11, 1848. https://doi.org/10.3390/app11041848

AMA Style

Hou P-J, Lee C-Y, Ou K-L, Lan W-C, Chuo Y-C, Lin H-Y, Chao H-W, Huang B-H, Saito T, Tsai H-Y, et al. Calcium Release from Different Toothpastes after the Incorporation of Tricalcium Phosphate and Amorphous Calcium Phosphate. Applied Sciences. 2021; 11(4):1848. https://doi.org/10.3390/app11041848

Chicago/Turabian Style

Hou, Ping-Jen, Chang-Yu Lee, Keng-Liang Ou, Wen-Chien Lan, Yen-Chun Chuo, Hung-Yang Lin, Hsiao-Wei Chao, Bai-Hung Huang, Takashi Saito, Hsin-Yu Tsai, and et al. 2021. "Calcium Release from Different Toothpastes after the Incorporation of Tricalcium Phosphate and Amorphous Calcium Phosphate" Applied Sciences 11, no. 4: 1848. https://doi.org/10.3390/app11041848

APA Style

Hou, P.-J., Lee, C.-Y., Ou, K.-L., Lan, W.-C., Chuo, Y.-C., Lin, H.-Y., Chao, H.-W., Huang, B.-H., Saito, T., Tsai, H.-Y., Yang, T.-S., Walinski, C. J., & Ruslin, M. (2021). Calcium Release from Different Toothpastes after the Incorporation of Tricalcium Phosphate and Amorphous Calcium Phosphate. Applied Sciences, 11(4), 1848. https://doi.org/10.3390/app11041848

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop