Dental Materials (2005) 21, 739748

[Link]/journals/dema

Novel amino acid modied zinc polycarboxylates for improved dental cements
Dong Xie*, Mona Faddah, Jong-Gu Park
Department of Biomedical Engineering, Purdue School of Engineering and Technology, Indiana UniversityPurdue University at Indianapolis, Indianapolis, IN 46202, USA
Received 23 September 2004; accepted 11 January 2005

KEYWORDS
Amino-acid modied; Zinc polycarboxylate; Dental cements

Summary Objective. The objective of this study was to develop a novel amino acid modied zinc/calcium polycarboxylate cement system, formulate the cements, and evaluate their mechanical strengths. Materials and methods. Acrylate and methacrylate derivatives of four amino acids were synthesized and characterized using FT-IR and 1HNMR spectroscopy. The derivatives were formulated with polymer having pendent methacrylate group, water, and synthesized novel ller. Compressive (CS) as well as exural strengths (FS) and viscosities of the resin liquids were used as tools to evaluate the formulations and formed cements. The specimens for CS and FS tests were conditioned in distilled water at 37 8C for 24 h and 7 d, respectively, prior to testing. Results. The measured CS and FS of the cements was in the decreasing order of methacryloyl beta-alanineOacryloyl glutamic acidZacryloyl beta-alanineOmethacryloyl glutamic acidO2-hydroxyethyl methacrylate. Methacryloyl beta-alanine was selected for further formulations due to its relatively low solution viscosity and high CS as well as FS. Effects of polymer content, P/L ratio, tartaric acid and initiator concentration were signicant. During aging, the cement showed a constant increase in CS for up to 1 month and then kept constant for up to 3 months. Conclusions. This study developed a novel amino acid modied zinc/calcium polycarboxylate cement system. This system was 85% higher in CS, 98% higher in DTS and 183% higher in FS, compared to Durelon. Q 2005 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Introduction
Zinc polycarboxylate cement is a water-based material that hardens following an acid-base
* Corresponding author. Tel.: C1 317 274 9748; fax: C1 317 278 2032. E-mail address: dxie@[Link] (D. Xie).

reaction between zinc-rich glass powder and an aqueous solution of poly(acrylic acid) [1,2]. Since its invention in 1968, zinc polycarboxylate cement has been widely used to cement inlays and crowns and to make bases [3]. The main advantage of this cement lies in its strong adhesion to dentin. However, its working time (less than 12 min) and compressive strength (4070 MPa) are relatively low

0109-5641/$ - see front matter Q 2005 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved. doi:10.1016/[Link].2005.01.008

740 [35], which allows the cement to be used only as base or cementing restorative. Two reasons are responsible for the above drawbacks. One is attributed to the fast setting nature of the reaction between zinc cations and poly(acrylic acid) anions and the other is probably due to the high molecular weight of polyacid that has been used in the cement. The poly(acrylic acid), is usually an aqueous solution with 4050% solid content and a molecular weight of 40,00050,000 Da, which leads to a high viscosity of the aqueous solution, difculty in mixing, and thus lower compressive strength and adhesion due to the inclusion of air bubbles in the course of mixing [6]. Attempts have been made to overcome these drawbacks by modifying polycarboxylic acid using copolymers of acrylic acid [7] and adding poly(vinyl phosphonic acid) [8] or by incorporating various llers into the zinc-containing glass using aluminium uoride [9], silicon dioxide [6], magnesium oxide [10], etc. However, the mechanical strengths are still relatively low as compared to other dental restorative cements. Glass-ionomer cements are being used as a luting cement and core restoratives due to their relatively high compressive strength and suitable adhesion. These cements are composed of calcium uoroaluminosilicate glass powder and an aqueous solution of polyacid [11]. Like zinc carboxylate cement, glass-ionomer cement is also a water-bas ed material that hardens following an acid-base reaction between aluminum/calcium cations and polyacid [12]. Two versions have been developed for glass-ionomer cements: conventional, which is similar to zinc polycarboxylate cement except for the calcium uoroaluminosilicate ller, and resinmodied, which not only contains carboxylic acid but also has pendent methacrylate on a polymer backbone [13]. Conventional glass-ionomer cement usually exhibit lower mechanical strengths compared to resin-modied glass-ionomer cement because the latter has both ionic bonds and polymerizable covalent bonds for crosslinking [13]. In most dental resin-modied glass-ionomer cements, 2-hydroxyethyl methacrylate (HEMA) is often used as a comonomer to render the resinmodied polyacid compatible with water [14,15]. However, HEMA was believed to cause potential cytotoxicity to the surrounding tissue if it is not completely polymerized [16]. Aluminum is a major component of the ller in glass-ionomer cements and it plays a key role in the high mechanical strengths exhibited by glass-ionomer cements. However, there has been a controversial issue regarding cytotoxicity of aluminum ions in the composition of glass-ionomer cements [17]. The zinc cation has been found to be very

D. Xie et al. osteoconductive and to stimulate osteogenesis [18,19]. In this study, the authors propose to develop a novel zinc/calcium resin-modied polycaboxylate cements by using newly synthesized llers and polymer matrix combined with amino acid derivatives as a comonomer for higher mechanical strengths and extended working time. The objective of this study was to synthesize a novel zinc/calcium based glass, amino acid derivatives and polyacid with pendent methacrylate, use them to formulate the cements, and evaluate the mechanical strengths of the formed cements. Effects of polymer content, P/L ratio, tartaric acid, initiator concentration, activator concentration and aging of the cements were studied.

Materials and methods

Materials
Zinc oxide (ZnO), tartaric acid, potassium persulfate (K2S2O8), ascorbic acid, cellulose acetate butyrate, g-(trimethoxysilyl)propyl methacrylate (TMSPMA), acrylic acid (AA), itaconic acid (IA), glutamic acid (GA), methacryloyl chloride (MC), acryloyl chloride (AC), beta-alanine (BA), 2-hydroxyethyl methacrylate (HEMA), sodium hydroxide (NaOH), ethyl acetate, anhydrous magnesium sulfate (MgSO4), butylated hydroxy toluene (BHT), hydrochloric acid (HCl, 37%), tetrahydrofuran (THF), diethyl ether, and methanol were used as received from Acros/Fisher Scientic Inc. (Pittsburgh, PA USA) without further purication. Calcium phosphate tribasic [Ca 10 (OH) 2 (PO4 )6 ] or hydroxyapatite (HA) and silicon (IV) oxide (SiO2) were used as received fro m Alfa Aesar Co. (Ward Hill, MA, USA). Strontium uoride (SrF2), 2,2 0 Azobisisobutyronitrile (AIBN), dibutyltin dlaurate (DBTL), triphenylstibine (TPS), and 2-isocyanatoethyl methacrylate (IEM) were received from Aldrich Chemical Co. (Milwaukee, WI, USA). Durelon (zinc pocarboxylate cement) was supplied by ESPE Dental Company address please.

Synthesis and preparation

Synthesis of amino acid derivatives
To a three-neck ask containing BA (6.67 g) and NaOH (6.0 g) aqueous solution, AC (6.1 ml) was added with stirring at a temperature below 5 8C [20]. After the reaction was completed, the mixture was acidied to pHZ2 with HCl and extracted with

Amino acid modied zinc polycarboxylates cements ethyl acetate. The extract containing acryloyl BA (ABA) was dried with MgSO4 and concentrated via a rotary evaporator to obtain white crystals. The same procedure s were used to synthesize methacryloyl BA (MBA), methacryloyl GA (MGA), and acryloyl GA (AGA).

741 the ball mill and sieved to obtain ne particles having a size equal to or less than 63 mm. The sieved llers were then treated with silane (TMSPMA)methanol solution, followed by heat-treatment at 110 8C.

Microencapsulation of ascorbic acid Synthesis of polyalkenoate with pendent methacrylate group

To a three-neck ask containing AIBN (0.052 g) and 12.5 ml of THF, a mixture of AA (2.74 ml), IA (1.3 g), MGA (1.07 g) and 15 ml of THF was added dropwise [21]. Under a nitrogen blanket, the reaction was initiated and run at 62 8C for 10 h. The solution was then cooled down to 40 8C. To the above solution, a mixture of 2.71 g of IEM, 2.7 ml of THF, 0.009 g of BHT, 0.009 g of TPS and 0.06 g of DBTL was added dropwise [21]. An additional 4-h period was used to complete the reaction. Both Fourier transform-infrared (FT-IR) and proton nuclear magnetic resonance (1HNMR) spectroscopy were used to monitor the reaction. The IEM grafted polymer was recovered by precipitation from diethyl ether, followed by drying in a vacuum oven at room temperature. To a ask containing 0.2 g of cellulose acetate butyrate and 20 ml of ethyl acetate, 0.1 g of ascorbic acid was added and suspended in the solution by stirring. Then 15 ml of n-hexane was added. After completing the addition, the ask was cooled with cold water to harden the formed microcapsules. The microcapsules were further washed with cold n-hexane, recovered by decantation and air-drying, and stored prior to use [23].

Formulation of cements
A two-component system (liquid and powder) was used to formulate the cements. The liquid component was prepared by mixing the polymer (50%, by weight) with K2S2O8 (0.25%), tartaric acid (TA, 1.0%), comonomer (25%) and distilled water (25%) unless otherwise specied. The powder was prepared by mixing the llers with encapsulated ascorbic acid (0.3% of ller, by weight), using a vortex vibrator. A powder/liquid ratio (P/L) of 12.5 was used in the formulation. Unless otherwise specied, the following formulation was used throughout the study: P/L ratioZ2/1 (by weight); liquid formulationZ50/25/25 (polymer/comonomer/water, by % weight); K2S2O8Z0.25%; TAZ1%; and encapsulated ascorbic acidZ0.3%.

Characterization of amino acid derivatives and polymer

The synthesized monomers were characterized using a melting point test apparatus (Mel-Temp II, Laboratory Devices, Inc., Holliston, MA, USA), FT-IR and NMR. The polymer was identied by FT-IR, NMR and gel permeation chromatography (GPC). FT-IR spectra were obtained with a FT-IR spectrophotometer (Mattson Research Series FT/IR 1000, Madison, WI, USA). 1HNMR spectra were obtained on a Bruker AM 400 MHz NMR analyzer using deuterated methyl sulfoxide as a solvent. Molecular weight [both number average molecular weight (Mn) and weight average molecular weight (Mw)] was estimated on a Waters GPC unit (Model 410 differential refractometer, Waters Inc., Milford, MA, USA), using standard GPC techniques and polystyrene as a standard. THF was used as a solvent.

Evaluation
Estimates of curing time
A metal rod was used to evaluate the curing time (or working time) [24]. The rod was inserted into the center of the cement mixture, which was mixed and packed into a two-ended open glass tube with diameter of 4 mm. Curing time was taken as the period from which the mixing process was initiated to the moment at which the metal rod could not be moved by hand.

Preparation of reactive inorganic ller

A glass mixture comprising HA, SrF2, ZnO and SiO2 in a ratio of 47:6:35:12 (by weight) was thoroughly mixed using a vortex vibrator, ground in a ball mill, sintered at 1400 8C for 3 h, and then quenched in water [22]. The sintered ller was ground again in

Viscosity determination
The viscosity of the liquid formulated with the polymer, amino acid derivative and distilled water was determined at 23 8C using a programmable

742 cone/plate viscometer (RVDV-IICCP, Brookeld Eng. Lab., Inc., Middleboro, MA, USA).

D. Xie et al. b the breadth of the specimen, and d the depth of the specimen.

Strength measurement
Specimens were mixed and fabricated at room temperature, according to the published protocol [25]. Briey, the cylindrical specimens were prepared in glass tubing with dimensions of 4 mm in diameter by 8 mm in length and 4 mm in diameter and 2 mm in thickness for compressive (CS) and diametral tensile strength (DTS) tests, respectively. The specimens for the exural strength (FS) test were prepared using a rectangular Teon mold with dimensions of 3 mm in width by 3 mm in depth by 25 mm in length. The specimens were removed from molds after 1530 min, and conditioned in distilled water at 37G2 8C for 24 h, prior to testing. Testing of specimens was performed on a hydraulic mechanical testing machine (Model 858 Mini Bionix, MTS Systems Corp., Eden Prairie, MN, USA), with a crosshead speed of 1 mm/min for CS, DTS and FS measurements. The FS test was performed in three-point bending, with a span of 20 mm between supports. The sample sizes were nZ68 for each test. CS was determined using an equation of CSZ P/pr2, where P is the load at fracture and r the radius of the cylinder, and DTS was determined from the relationship DTSZ2P/pdt, where P is the load at fracture, d the diameter of the cylinder and t the thickness of the cylinder. The exural strength in three-point bending was obtained using the expression FSZ3Pl/2bd2, where P the load at fracture, l the distance between the two supports,
Table 1 Code MGA

Statistical analysis
One-way analysis of variance (ANOVA) with the post hoc TukeyKramer multiple range test was used to determine signicant differences of strengths among the materials in each group. A level of aZ0.05 was used for statistical signicance.

Results
Synthesis and characterization of amino acid derivatives and polymer with pendent methacrylate
The measured melting points, FT-IR and 1HNMR spectra, and yields of the synthesized amino acid derivatives were identied in Table 1. MGA, AGA, MBA and ABA showed their melting points at 121, 119, 69 and 95 8C and their yield at 8593, 5259, 73 80 and 6370%, respectively. All the derivatives exhibited strong FT-IR peaks at around 17211731 (CaO stretching), 16571755 (CaC stretching conjugated with CaO) as well as 983933 (CaC out of plane bending), 16211604 (CaO stretching), and 15531534 cmK1 (NH bending) associated with carbonyl group, carboncarbon double bond, amide I bond, and amide II bond, respectively. All the derivatives also showed strong and broad bands ranging from 3600 to 2400 cmK1 (OH stretching at 33002500, NH stretching at 31002070 and CH stretching at 29602930) for hydroxyl group on

Yield, melting point, FT-IR and 1HNMR of synthesized amino acid derivatives and grafted copolymer. Melting point (8C) 120.8121.5 Yield (%) 8593 FT-IR (cmK1) 36002400 (NH, COOH, CH3), 1722 (CaO), 1656 (CaC), 1607 (amide I), 1534 (amide II), 936 (CaC) 36002400 (NH, COOH, CH3), 1721 (CaO), 1655 (CaC), 1604 (amide I), 1539 (amide II), 933 (CaC) 36002400 (NH, COOH, CH3), 1722 (CaO) 1657 (CaC), 1613 (amide I), 1547 (amide II), 1120 980 (CaC) 36002400 (NH, COOH, CH3), 1719 (CaO) 1655 (CaC), 1621 (amide I), 1553 (amide II), 983 (CaC) 34002600 (NH, COOH, CH3), 1715 (CaO) 1649 (amide I), 1638 (CaC) HNMR (ppm) 12.80 (COOH), 8.60 (amide), 5.75 and 5.42 (CaC) 12.20 (COOH), 8.60 (amide), 5.65 and 5.32 (CaC) 12.80 (COOH), 8.60 (amide), 6.25 and 5.75 (CaC) 12.20 (COOH), 8.60 (amide), 6.15 and 5.70 (CaC) 12.57 (COOH), 8.31 (amide), 5.67 and 6.08 (CaC)
1

MBA

69.769.9

7380

AGA

118.5119.5

5259

ABA

95.096.0

6370

Grafted copolymer

94

Amino acid modied zinc polycarboxylates cements carboxyl groups, NH from amide groups and CH from CH3. For 1HNMR, the methacrylate derivatives exhibited typical chemical shifts at around 5.755.65 and 5.425.32 ppm for carboncarbon double bonds, whereas the acrylate derivatives showed multiple chemical shifts at a higher eld, i.e. 6.256.15 and 5.755.70 ppm for carboncarbon double bonds, in addition to 8.60 ppm for amide and 12.2012.80 ppm for carboxyl group. For the polymer (Table 1), there are four typical peaks on FT-IR at around 34002600, 1715, 1649 and 1638 cmK1 for OH on carboxyl, NH from amide as well as CH from methyl, carbonyl, amide, and double bonds, respectively. The 1HNMR chemical shifts of carboxyl, amide, and double bonds were found at 12.57, 8.31, and 5.67 as well as 6.08 ppm, respectively. The yield for the polymer was 94%. The molecular weights for the polymer were 5300 Da for number average (Mn) and 15,000 Da for weight average (Mw) with PDI (polydispersity index) of 2.83.

743

Figure 2 Effect of liquid formulation on CS, FS and viscosity. P/LZ2.0/1; ComonomerZMBA; The cements were conditioned in distilled water at 37 8C for 1 day for CS and 1 week for FS.

Formulation and evaluation of cements

Compressive strength (CS) and viscosities were used as screen tools to evaluate the formed cements. Fig. 1 shows the CS and FS of the cements and viscosities of the polymer liquids composed of four amino acid derivatives and HEMA. The liquid formulation was 50/ 25/25 based on polymer/comonomer/water and the P/L ratio was 2.0/1. The CS (MPa) was in the decreasing order of MBA (113.6G9.2)OABA (103.1G5.27)OAGA (102.8G2.9)OMGA (97.4G 2.87)OHEMA (82.4G6.8), where MBA, ABA and AGA; ABA, AGA and MGA were not signicantly different from each other (pO0.05). The FS (MPa) was in the decreasing order of MBA (48.6G3.9)OAGA

Figure 1 CS and FS of all the cements and the viscosities of the corresponding resin liquids. Liquid formulationZ50/25/25 (polymer/comonomer/water); P/L ratioZ2.0/1; The cements were conditioned in distilled water at 37 8C for 1 day for CS and 1 week for FS.

(46.2G6.0)OABA (41.2G5.4)OMGA (40.6G5.7)O HEMA (25.7G2.6), where MBA, ABA, AGA and MGA were not signicantly different from each other (pO 0.05). The viscosity (!10K3 cp) of the liquid was in the decreasing order: MGA (5.3)OAGA (4.2)OABA (1.2)OMBA (0.99)OHEMA (0.32). Fig. 2 shows the effect of liquid formulation on CS, FS and viscosity. Both CS and FS (MPa) were in the decreasing o rder of 50/25/25 (113.6G9.2) O55/20/25 (110.3G4.6)O40/30/30 (93.9G 4.2)O30/35/35 (79.9G9.7) and 55/20/25 (45.3G5.4)O50/25/25 (42.4G4.4)O40/30/30 (32.1G3.4)O30/35/35 (28.7G2.6), respectively. There were no signicant differences in CS between 55/20/25 and 50/25/25, in FS between 55/20/25 and 50/25/25, and in FS between 40/30/30 and 30/ 35/35 (pO0.05). Viscosities (cp!10K3) for different formulations were in the decreasing order of 55/20/25 (1.02)O50/25/25 (0.99)O40/30/30 (0.15)O30/35/35 (0.05). Fig. 3 shows the effect of P/L ratio on CS and FS. Both CS and FS of the cement were increased with an increase of P/L ratio. CS and FS (MPa) were in the decreasing order of 2.5/1 (134.6G11.9)O2.0/1 (113.6G9.2)O1.5/1 (94.2G3.3)O1.0/1 (76.7G 4.5) and 2.5/1 (57.3G3.2)O2.0/1 (48.6G3.9) O1.5/1 (41.5G3.7)O1.0/1 (28.8G3.9), respectively. There were no signicant differences in CS and FS among different P/L ratios (pO0.05). The effect of tartaric acid (TA) on CS and curing time (CT) is shown in Fig. 4. With the increase of TA, the CS was signicantly reduced but the CT was signicantly increased. CS (MPa) and CT (min) were in the order of (decreasing) 146.2G4.2O117.4G8.9O 96.5G3.5O86.9G6.1 and (increasing) 1.3!3.9! 7.8!12.0!29.5, respectively, for 0, 1, 3, 5 and 8% TA. The CS values for these cements were signicantly

744
Table 2 and CT.

D. Xie et al.
Effects of K2S2O8 and ascorbic acid on CS CS (S.D.) (MPa) (5.1) (3.7)a (4.4)a (5.5)a (1.3) (3.7)b (3.6)b (4.4) Curing time (min) 3.3 4.2 4.5 6.7 7.1 4.2 4.1 3.5

Concentration (%, by weight)

Figure 3 Effect of P/L ratio on CS and FS. Liquid formulationZ50/25/25; ComonomerZMBA; The cements were conditioned in distilled water at 37 8C for 1 day for CS and 1 week for FS.

Effect of K2S2O8 0.10 98.5 0.25 120.0 0.40 113.2 0.55 113.0 Effect of ascorbic acid 0.60 108.0 0.90 120.5 1.20 114.4 1.50 101.5

different from one another in statistics (p!0.05), except for the cements with TA between 3 and 5%. The effects of initiator potassium persulfate and activator ascorbic acid on CS and CT are shown in Table 2. With increasing K2S2O8, both CS and CT were increased. CS (MPa) and CT (min) were in the order of (increasing) 98.5G5.1!120.0G3.6! 113.2G4.4Z113.0G5.5 and (increasing) 3.3! 3.8!4.5!6.7, respectively, for 0.1, 0.25, 0.4 and 0.55% for K2S2O8. No signicant differences were found among 0.25, 0.4 and 0.55% (pO0.05). With increasing ascorbic acid in the course of 0.6, 0.9, 1.2 and 1.5%, the CS increased rst and then decreased but CT decreased, with corresponding values of 108.0G1.3, 120.5G3.7, 114.4G3.6 and 101.4G4.4 for CS (MPa) and of 7.1, 4.2, 4.1 and 3.5 for CT (min), respectively. There was no signicant difference between 0.9 and 1.2% (pO0.05). Fig. 5 shows CS, DTS and FS of the optimal experimental cement and commercial zinc carboxylate cement Durelon after conditioning in distilled
160 140 120 35 30 25 20 80 15 60 40 20 0 0% 1% 3% 5% 8% 10 5 0

Entries are mean values with standard deviations in parentheses; the mean values with the same superscript letter were not signicantly different (pO0.05).

water at 37 8C for 1 week. The experimental cement exhibited signicantly higher CS (139.1G 4.8 MPa), DTS (24.3G2.1 MPa) and FS (60.5G 8.8 MPa), compared to corresponding 75.3G5.4, 12.3G0.8 and 21.4G1.2 for Durelon. Fig. 6 shows the effect of aging on CS over a period of three months. The CS (MPa) increased from 72.5G1.7 (1 h) to 139.1G4.8 (1 w) and to 157.8G4.2 (1 m) and then remained constant up to 3 months (158.1G7.8).

Discussion
Synthesis and characterization
Among four synthesized amino acid derivatives (Table 1), the yields for methacrylate derivatives of the amino acids, MBA (7380%) and MGA (8593%),

CS (MPa)

CT (min)

100

Figure 4 Effect of tartaric acid concentration on CS and CT. Liquid formulationZ50/25/25; ComonomerZMBA; P/L ratioZ2.0/1; The cements were conditioned in distilled water at 37 8C for 1 day for CS and 1 week for FS.

Figure 5 CS, DTS and FS of the optimal experimental cement and Durelon. The cements were conditioned in distilled water at 37 8C for 1 week. For experimental cement, comonomerZMBA; Liquid formalutionZ 50/25/25; P/L ratioZ2.0/1. For Durelon, P/LZ1.5/1.

Amino acid modied zinc polycarboxylates cements

180 160 140 120 100 80 60 40 20 0 1h 1d 1w 1m 3m

745 anions [27]. To extend the working time, other components such as magnesium oxide, aluminum uoride, etc. have been added [9,10]. In this study, calcium phosphate was incorporated for potentially improved biocompatibility; silicon oxide was added for enhancing glass network formation; and strontium uoride was used for radiopacity and uoride release. The sintered glass was treated with a silane agent for enhanced ller compatibility with polymer resin [3]. The authors found that both sintering and silanization signicantly improved mechanical strengths [28]. Due to the introduction of the in situ polymerizable reactive pendent carbon-carbon double bonds, it is necessary to nd a suitable initiation system to accomplish in situ polymerization. In this study, a water-compatible redox initiation system was introduced to the novel modied zinc-containing cement system. It is impossible to apply a popular photo-initiator system that has been commonly used in dental composites or glass-ionomer cements, due to the very opaque characteristics of the zinc-containing cement. It is well known that benzoyl peroxide and N, N 0 -dimethyl-p-toluidine are hydrophobic redox initiators for dentures [3]. In the case of water-based resin cements, such as resin-modied glass-ionomer cements, so far little work on redox-initiator systems has been reported. In addition, it was found to be impossible to initiate in situ polymerization just by simply mixing watersoluble redox initiators with water-soluble polymer resin system because setting was too fast to allow the cement to be mixed well. The setting often occurred in seconds. To overcome the difculty in manipulation, ascorbic acid (activator) was microencapsulated with cellulose acetate butyrate to allow an extended working or curing time. After microencapsulation, the curing time was extended up to around 7 min (Table 2).

Figure 6 Effect of aging on CS. Liquid formulationZ 50/25/25; ComonomerZMBA; P/L ratioZ2.0/1; The cements were conditioned in distilled water at 37 8C prior to testing.

were higher than those for their acrylate counterparts, ABA (6370%) and AGA (5259%). The reason may be attributed to the hydrophobic methyl group on the methacryloyl amino acids, since this group makes these amino acids more hydrophobic. When the synthesized amino acid derivatives were recovered from aqueous solution to ethyl acetate, the difference of hydrophilicity between the two types of derivatives led to the yield difference. For melting point, MBA was the lowest and MGA was the highest. M GA and AGA exhibited a close melting point and both were higher in melting point than MBA and ABA, which may be attributable to stronger intermolecular hydrogen bonding in the former, since MGA and AGA have two carboxyl groups per molecule. ABA showed a higher melting point than MBA, which may be explained as the existence of intramolecular hydrogen bonding in the latter. Terpolymer grafted with pendent methacrylate was synthesized as reported [21,26]. For the grafting reaction, in situ disappearance of the isocyanate (NCO) peak from IEM at around 2271 cmK1 and formation of the carbon-carbon double bond at 1638 cmK1 conrmed the completion of the reaction.

CS (MPa)

Amino acid derivatives as a comonomer

In this study, CS, FS and viscosity measurements were used to evaluate the cements formulated with amino acid derivatives. Viscosity measurement was used to quickly determine which formulation would be workable for use in dental clinics [29], if the strength values given are much the same. From Fig. 1, MBA showed the highest CS as well as FS and the lowest viscosity among four amino acid derivatives. HEMA showed the lowest CS, FS and viscosity, which can be attributed to no acid contribution to the salt-bridge formation, thus leading to a lower strength. In the case of amino acid derivatives, ABA, AGA as well as MGA and ABA, MBA and AGA

Formulation and evaluation of cements

Filler and cement preparations
Four components including zinc oxide, calcium phosphate, silicon oxide and strontium uoride were used to prepare the reactive llers. It is known that zinc polycarboxylate cement is low in mechanical strengths and short in working time (usually less than 1 min) due to the quick setting reaction between zinc cations and polycarboxylic acid

746 were statistically the same in CS and ABA. AGA, MBA, ABA and MGA were statistically the same in FS. However, based on the viscosity and absolute CS and FS values, it seems that MBA was the best candidate for further formulations because the cement formulated with MBA (113.6 MPa) exhibited the lowest viscosity (0.99) of all, which may be attractive to clinicians.

D. Xie et al. The ratio of 2.0/1 is recommended as probably acceptable in dental practice.

Effect of tartaric acid

Incorporating tartaric acid (TA) into dental glassionomer cements has been found to be very effective in extending working time, especially for conventional glass-ionomers [11,34,35]. It has been postulated that in the presence of tartaric acid, metal ions react preferentially with tartaric acid to form tartrate, leading to a delay of the formation of polyacid-metal ion salt-bridges [35]. This concept was borrowed and brought to this study to extend the curing time, and data conrmed this theory. With the increase of TA, the CT signicantly increased from 1.3 to 29.5 min, accompanying a loss of the CS from 146.2 to 73.4 MPa (Fig. 4). This can be interpreted as a plastisizer effect because in the polymer industry small molecules are often added as a plasticizer for better processing, which leads to a reduction in mechanical strengths [36]. That is why the excessive amount of tartaric acid decreased CS even though it extended the working time dramatically. Thus tartaric acid should be added in such a way that it would not signicantly reduce the mechanical strengths but still provide comfortable manipulation.

Effect of polymer content

In the experimental cement, there were three main liquid components in its composition: resin modied polyacid, amino acid derivative and water. It is impossible if any either of them is missing. Modied polymer provides main mechanical strength; amino acid derivative is not only a comonomer but also acts to enhance compatibility to bring the resinmodied polyacid into water, since the modied polyacid is not very water soluble [13,30]. Water acts as a reaction medium for the salt-bridge formation [11,13]. Theoretically speaking, the more polymer in the formulation, the higher the mechanical strengths [11]. As shown in Fig. 2, strength values (CS and FS) and viscosities increased with increasing polymer content. However, the formulation with 50/25/25 showed the highest CS and FS among the different liquid formulations, with a workable viscosity as compared to 55/20/25. The formulation with 60/20/20 did not work, due to substantially high viscosity. Neither 55/20/25 not 60/20/20 gave the highest strengths, which was probably due to difcult polymerization propagation because of diffusion problems, thus causing low conversion.

Effect of initiators
During the study, the authors found that both potassium persulfate and ascorbic acid exerted effects on mechanical strength and curing time. As shown in Table 2, CS and CT were increased with increasing K2S2O8 in the presence of the same concentration of ascorbic acid. In contrast, with increasing microencapsulated ascorbic acid, CS was increased at the beginning and then decreased, but CT decreased. The reason may be attributed to poor mixing of the specimens due to a short curing time. The best concentrations for K2S2O8 and ascorbic acid were 0.25 and 0.9%, respectively. The CS and CT for this initiator pair were 120.0 MPa and 4.2 min, respectively. It is concluded that microencapsulation extends the working time and makes the water-soluble initiator system workable.

Effect of P/L ratio

P/L ratios are very important in dental cements. Higher P/L ratio usually exhibits higher mechanical strength, especially CS [11,31,32], but it also shortens working time [33]. Using the same liquid formulation (50/25/25), the authors formulated cements with P/L ratios of 2.5/1, 2.0/1, 1.5/1 and 1.0/1. 2.5/1 was the highest ratio, which could be dealt with because a higher ratio made the cement preparation impossible. As shown in Fig. 3, the lowest P/L ratio gave the lowest CS and FS. Both CS and FS increased with the increase in the P/L ratio. CS increased even more signicantly, which was consistent with the theory that brittle materials tend to show a higher CS [31,32]. However, the authors found that the ratio of 2.5/1 was not suitable to dental clinics due to relatively difcult manipulation during specimen preparation.

Comparison between the experimental and commercial cements

As shown in Fig. 5, the experimental cement exhibited 85% higher CS, 98% higher DTS and 183% higher FS than commercial cement Durelon. The signicantly enhanced strengths are attributed to

Amino acid modied zinc polycarboxylates cements improved polymer-ller networks. The resin-modied polycarboxylic acids are mainly responsible for signicantly high mechanical strengths, especially FS. This experimental cement may be a potential replacement for current commercially available zinc carboxylate cements.

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References
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Aging
It is known that glass-ionomer cements increase their strengths with time due to constant saltbridge formations [37]. No exception was found for the experimental cements in this study because the cements were composed of zinc/calcium cations and modied polycarboxylates. The experimental cements selected were conditioned in water for 1 h, 1 day, 1 week, 1 and 3 months, followed by CS determinations. Results show that the CS signicantly increased from 1 h at 72.5 to 1 m at 157.8 MPa and then remained constant for up to 3 months (Fig. 6), which reects the characteristics of this type of composites.

Conclusions
Novel amino acid modied hybrid zinc/calcium polycarboxylate cements have been developed. This system exhibited signicantly higher mechanical strengths, as compared to commercial zinc polycarboxylate cement, Durelon. Among the amino acid derivatives investigated, methacryloyl beta-alanine was considered to be the most promising candidate for further evaluation. Effects of polymer content, P/L ratio, tartaric acid, initiator concentration and activator concentration were signicant. It was found that an appropriate ratio balance between these parameters is very important. Aging study shows that the experimental cement showed a constant increase in mechanical strength for up to 1 month and then kept constant, which is of great clinical importance. Future research will focus on the evaluation of adhesion to tooth, biocompatibility and other properties of these novel cements.

Acknowledgements
This work was sponsored by National Institute of Biomedical Imaging and Bioengineering (NIH Grant No. 1R01 EB03162-01).

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