Bis-GMA co-polymerizations: Influence on conversion, flexural properties, fracture toughness and susceptibility to ethanol degradation of experimental composites

Objectives. The aim of this study was to evaluate the influence of monomer content on fracture toughness (K(Ic)) before and after ethanol solution storage, flexural properties and degree of conversion (DC) of bisphenol A glycidyl methacrylate (Bis-GMA) co-polymers. Methods. Five formulations were tested, containing Bis-GMA (B) combined with TEGDMA (T), UDMA (U) or Bis-EMA (E), as follows (in mol%): 30B:70T; 30B:35T:35U; 30B:70U; 30B:35T:35E; 30B:70E. Bimodal filler was introduced at 80 wt%. Single-edge notched beams for fracture toughness (FT, 25 mm x 5 mm x 2.5 mm, a/w = 0.5, n = 20) and 10 mm x 2 mm x 1 mm beams for flexural strength (FS) and modulus (FM) determination (10 mm x 2 mm x 1 mm, n = 10) were built and then stored in distilled water for 24 h at 37 degrees C. All FS/FM beams and half of the FT specimens were immediately submitted to three-point bending test. The remaining FT specimens were stored in a 75%ethanol/25%water (v/v) solution for 3 months prior to testing. DC was determined with FT-Raman spectroscopy in fragments of both FT and FS/FM specimens at 24 h. Data were submitted to one-way ANOVA/Tukey test (alpha = 5%). Results. The 30B:70T composite presented the highest K(Ic) value (in MPa m(1/2)) at 24 h (1.3 +/- 0.4), statistically similar to 30B:35T:35U and 30B:70U, while 30B:70E presented the lowest value (0.5 +/- 0.1). After ethanol storage, reductions in K(Ic) ranged from 33 to 72%. The 30B:70E material presented the lowest reduction in FT and 30B:70U, the highest. DC was similar among groups (69-73%), except for 30B:70U (52 +/- 4%, p < 0.001). 30B:70U and 30B:35T:35U presented the highest FS (125 +/- 21 and 122 +/- 14 MPa, respectively), statistically different from 30B:70T or 30B:70E (92 +/- 20 and 94 +/- 16 MPa, respectively). Composites containing UDMA or Bis-EMA associated with Bis-GMA presented similar FM, statistically lower than 30B:35T:35U. Significance. Composites formulated with Bis-GMA:TEGDMA:UDMA presented the best compromise between conversion and mechanical properties. (C) 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Influence of BisGMA, TEGDMA, and BisEMA contents on viscosity, conversion, and flexural strength of experimental resins and composites

Different monomer structures lead to different physical and mechanical properties for both the monomers and the polymers. The objective of this study was to determine the influence of the bisphenylglycidyl dimethacrylate (BisGMA) concentration (33, 50 or 66 mol%) and the co-monomer content [triethylene glycol dimethacrylate (TEGDMA), ethoxylated bisphenol-A dimethacrylate (BisEMA), or both in equal parts] on viscosity (eta), degree of conversion (DC), and flexural strength (FS). eta was measured using a viscometer, DC was obtained by Fourier transfer Raman (FT-Raman) spectroscopy, and FS was determined by three-point bending. At 50 and 66% BisGMA, increases in eta were observed following the partial and total substitution of TEGDMA by BisEMA. For 33% BisGMA, eta increased significantly only when no TEGDMA was present. The DC was influenced by BisGMA content and co-monomer type. Mixtures containing 66% BisGMA showed a lower DC compared with mixtures containing other concentrations of BisGMA. The BisEMA mixtures had a lower DC compared with the TEGDMA mixtures. The FS was influenced by co-monomer content only. BisEMA mixtures presented a statistically lower FS, followed by TEGDMA + BisEMA mixtures, and then by TEGDMA mixtures. Partial or total replacement of TEGDMA by BisEMA increased eta, which was associated with the observed decreases in DC and FS. Although the BisGMA content influenced the DC, it did not affect the FS results.

Adhesive Temperature: Effects on Adhesive Properties and Resin-Dentin Bond Strength

Objectives: To evaluate the effect of adhesive temperature on the resin-dentin bond strength (mu TBS), nanoleakage (NL), adhesive layer thickness (AL), and degree of conversion (DC) of ethanol/water- (SB) and acetone-based (PB) etch-and-rinse adhesive systems. Methods: The bottles of the two adhesives were kept at each temperature (5 degrees C, 20 degrees C, 37 degrees C, and 50 degrees C) for 2 hours before application to demineralized dentin surfaces of 40 molars. Specimens were prepared for mu TBS testing. Bonded sticks (0.8 mm(2)) were tested under tension (0.5 mm/min). Three bonded sticks from each tooth were immersed in silver nitrate and analyzed by scanning electron microscopy. The DC of the adhesives was evaluated by Fourier transformed infrared spectroscopy. Results: Lower mu TBS was observed for PB at 50 degrees C. For SB, the mu TBS values were similar for all temperatures. DC was higher at 50 degrees C for PB. Higher NL and thicker AL were observed for both adhesives in the 5 degrees C and 20 degrees C groups compared to the 37 degrees C and 50 degrees C groups. The higher temperatures (37 degrees C or 50 degrees C) reduced the number of pores within the adhesive layer of both adhesive systems. Conclusions: It could be useful to use an ethanol/water-based adhesive at 37 degrees C or 50 degrees C and an acetone-based adhesive at 37 degrees C to improve adhesive performance.

In vitro wear, surface roughness and hardness of propanal-containing and diacetyl-containing novel composites and copolymers based on bis-GMA analogs

Objective. To evaluate the effect of two additives, aldehyde or diketone, on the wear, roughness and hardness of bis-GMA-based composites/copolymers containing TEGDMA, propoxylated bis-GMA (CH(3)bis-GMA) or propoxylated fluorinated bis-GMA (CF(3)bis-GMA). Methods. Fifteen experimental composites and 15 corresponding copolymers were prepared combining bis-GMA and TEGDMA, CH3bis-GMA or CF3bis-GMA, with aldehyde (24mol% and 32 mol%) or diketone (24 mol% and 32 mol%) totaling 30 groups. For composites, hybrid treated filler (barium aluminosilicate glass/pyrogenic silica; 60 wt%) was added to monomer mixtures. Photopolymerization was affected by 0.2 wt% each of camphorquinone and N,N-dimethyl-p-toluidine. Wear (W) test was conducted in a toothbrushing abrasion machine (n = 6) and quantified using a profilometer. Surface roughness (R) changes, before and after abrasion test, were determined using a rugosimeter. Microhardness (H) measurements were performed for dry and wet samples using a Knoop microindenter (n = 6). Data were analyzed by one-way ANOVA and Tukey`s test (alpha = 0.05). Results. Incorporation of additives led to improved W and H values for bis-GMA/TEGDMA and bis-GMA/CH(3)bis-GMA systems. Additives had no significant effect on the W and H changes of bis-GMA/CF(3)bis-GMA. With regard to R changes, additives produced decreased values for bis-GMA/CH3bis-GMA and bis-GMA/CF3bis-GMA composites. Bis-GMA/TEGDMA and bis-GMA/CH(3)bis-GMA copolymers with additives became smoother after abrasion test. Significance. The findings correlate with additives ability to improve degree of conversion of some composites/copolymers thereby enhancing mechanical properties. Published by Elsevier Ltd on behalf of Academy of Dental Materials

Color stability of silorane-based composites submitted to accelerated artificial ageing-An in situ study

Objectives: To assess the in situ color stability, surface and the tooth/restoration interface degradation of a silorane-based composite (P90, 3M ESPE) after accelerated artificial ageing (AAA), in comparison with other dimethacrylate monomer-based composites (Z250/Z350, 3M ESPE and Esthet-X, Dentsply). Methods: Class V cavities (25 mm(2) x 2 mmdeep) were prepared in 48 bovine incisors, which were randomly allocated into 4 groups of 12 specimens each, according to the type of restorative material used. After polishing, 10 specimens were submitted to initial color readings (Easyshade, Vita) and 2 to analysis by scanning electronic microscopy (SEM). Afterwards, the teeth were submitted to AAA for 384 h, which corresponds to 1 year of clinical use, after which new color readings and microscopic images were obtained. The values obtained for the color analysis were submitted to statistical analysis (1-way ANOVA, Tukey, p < 0.05). Results: With regard to color stability, it was verified that all the composites showed color alteration above the clinically acceptable levels (Delta E >= 3.3), and that the silorane-based composite showed higher Delta E (18.6), with a statistically significant difference in comparison with the other composites (p < 0.05). The SEM images showed small alterations for the dimethacrylate-based composites after AAA and extensive degradation for the silorane-based composite with a rupture at the interface between the matrix/particle. Conclusion: It may be concluded that the silorane-based composite underwent greater alteration with regard to color stability and greater surface and tooth/restoration interface degradation after AAA. (C) 2011 Elsevier Ltd. All rights reserved.

Availability of folate bound to folate-binding protein: Environmental effects

The effect of FBP on folate bio-availability depends on its environment. The FBP of whole WPC enhances bioavailability of folates more than does purified FBP and its efficacy might be even greater when lipids are removed from the WPC. FBP polymerises and folate release from the polymer is found to be slower than that from the monomer. FBP has a role also as a folate receptor at cell surfaces and in this role folate binding increases polymerisation of FBP attached to lipid membranes.

Studies of solute self-association by sedimentation equilibrium: allowance for effects of thermodynamic non-ideality beyond the consequences of nearest-neighbor interactions

A sedimentation equilibrium study of a-chymotrypsin self-association in acetate-chloride buffer, pH 4.1 I 0.05, has been used to illustrate determination of a dimerization constant under conditions where thermodynamic non-ideality is manifested beyond the consequences of nearest-neighbor interactions. Because the expressions for the experimentally determinable interaction parameters comprise a mixture of equilibrium constant and excluded volume terms, the assignment of reasonable magnitudes to the relevant virial coefficients describing non-associative cluster formation is essential for the evaluation of a reliable estimate of the dimerization constant. Determination of these excluded volume parameters by numerical integration over the potential-of-mean-force is shown to be preferable to their calculation by approximate analytical solutions of the integral for this relatively small enzyme monomer with high net charge (+ 10) under conditions of low ionic strength (0.05 M). (C) 2001 Elsevier Science B.V. All rights reserved.

Structural Dynamics in (ND4)2[Cu(D2O)6](SO4)2

The extended X-ray absorption fine structure spectroscopy (EXAFS) of (ND4)(2)[CU(D2O)(6)](SO4)(2) at 5, 14,100, 200, and 298 K is reported. This indicates that the Cu-O bond lengths of the Cu(D2O)(6)(2+) ion do not change significantly within this temperature range, which contrasts with EPR results and X-ray and neutron diffraction experiments, which imply that two of the Cu-(D2O) bonds converge in length as the temperature is raised. The EXAFS measurements thus confirm that the bond distances yielded by the diffraction experiments refer to the average positions of ligands involved in a dynamic equilibrium in which the directions of the long and intermediate bonds of the Jahn-Teller distorted Cu(D2O)(6)(2+) ion are interchanged in the crystal lattice. Analysis of the displacement parameters is consistent with this interpretation, as are the wave functions calculated using a model involving Jahn-Teller vibronic coupling and the influence of lattice strain interactions.

Diverse solid-state and solution structures within a series of hexaamine dicopper(II) complexes

Mono- and dicopper(II) complexes of a series of potentially bridging hexaamine ligands have been prepared and characterized in the solid state by X-ray crystallography. The crystal structures of the following Cu-II complexes are reported: [Cu(HL3)](ClO4)(3), C11H31Cl3CuN6O12, monoclinic, P2(1)/n, a = 8.294(2) Angstrom, b = 18.364(3) Angstrom, c = 15.674(3) Angstrom, beta = 94.73(2)degrees, Z = 4; {[Cu-2(L-4)(CO3)](2)}(ClO4)(4). 4H(2)O, C40H100Cl4Cu4N12O26, triclinic, P (1) over bar, a = 9.4888(8) Angstrom, b=13.353(1) Angstrom,. c = 15.329(1) Angstrom, alpha = 111.250(7)degrees, beta = 90.068(8)degrees, gamma = 105.081(8)degrees, Z=1; [Cu-2(L-5)(OH2)(2)](ClO4)(4), C(13)H(36)Cl(4)Cu(2)Z(6)O(18), monoclinic, P2(1)/c, a = 7.225(2) Angstrom. b = 8.5555(5) Angstrom, c = 23.134(8) Angstrom, beta = 92.37(1)degrees, Z = 2; [Cu-2(L-6)(OH2)(2)](ClO4)(4). 3H(2)O, C14H44Cl4Cu2N6O21, monoclinic, P2(1)/a, a = 15.204(5) Angstrom, b = 7.6810(7) Angstrom, c = 29.370(1) Angstrom, beta = 100.42(2)degrees, Z = 4. Solution spectroscopic properties of the bimetallic complexes indicate that significant conformational changes occur upon dissolution, and this has been probed with EPR spectroscopy and molecular mechanics calculations.

The radical homopolymerization of N-phenylmaleimide, N-n-hexylmaleimide and N-cyclohexylmaleimide in tetrahydrofuran

The kinetics and mechanisms of thermally initiated (using 2,2'-azobisisoburyronitrile (AIBN) as initiator) radical homopolymerizations of a series of maleimides, including N-phenymaleimide (PHMI) [l-phenyl-1H-pyrrole-2,5-dione]; N-n-hexylmaleimide (nHMI) [l-(n-hexyI)-1H-pyrrole-2,5-dione]; and N-cyclohexylmaIeimide (CHMI) [l-cyclohexyl- 1H-pyrrole-2,5-dione] have been investigated in THF solution by an on-line FT-NIR technique. It was found that the order of the activation energies for the three N-sub-MIs is: E-a PHMI < E-a (PHMI) < E-a (CHMI). The overall polymerization rate parameter k and the pre-exponential factor A were calculated. The kinetic order with respect to the N-sub-MIs was in the range of 0.71 < m < 0.75 for the initiator and n = 1.0 for the monomer. Radical transfer to solvent was found to be the key factor in determining the apparent order with respect to the initiator. All of the homopolymers had a relatively low molecular weight. The end groups of the polymer chains were characterized by MALDI-TOF, GPC and NMR methods and the results clearly indicate that the polymerization was initiated by THF radicals, and that the termination reaction is mainly controlled by chain transfer to solvent through an hydrogen abstraction mechanism. (C) 2001 Elsevier Science Ltd. All rights reserved.

Copolymerization of methyl methacrylate and allyl acetate Part I. Rate of reaction

Free radical bulk copolymerization of methyl methacrylate (MMA) and allyl acetate (AAc) has been investigated using electron spin resonance (ESR) and FT-near infrared (FTNIR) spectroscopy. Data are used to evaluate the rate constants. The mole fraction of AAc plays an important role in the copolymerization of these two monomers. AAc not only delays the Trommsdorff effect but also increases the onset of percentage total conversion at which the Trommsdorff region begins. With AAc fraction 0.5 and higher, no Trommsdorff effect was observed. Inclusion of AAc into copolymer structure mainly occurs in the Trommsdorf region or when the AAc fraction in the comonomer feed is dominant. This is associated with a drop in the concentration of propagating radicals. However, ESR spectra indicate that the MMA propagating radical is predominant during the reaction. In the comonomer mixtures where a Trommsdorff region can be observed, the addition of AAc does not produce any significant change in k(p) and k(t) in the steady state region. Major changes in k(p) and k(t) are observed after the gel point and glassy state, respectively. (C) 2001 Society of Chemical Industry.

Free-radical bulk polymerization of styrene: ESR and near-infrared spectroscopic study of the entire conversion range

The free radical polymerization of styrene in bulk was monitored by ESR and FT near-infrared spectroscopy at 70°C for a series of concentrations of the initiator, dimethyl 2,2′-azobis(isobutyrate). In order to obtain detailed kinetic information over the intire conversion range, and the gel effect range in particular, conversion and free radical concentration data points were accumulated with exceptionally short time intervals. The polystyrene radical concentration ([St•]) went through a sharp maximum at the gel effect, a feature that has hitherto escaped observation due to the rapid concentration changes in the gel effect range relative to the data point time intervals of previous studies. Temperature measurements throughout the polymerization were employed to calculate that a temperature increase was not the cause of the [St•] maximum, which thus appeares to be a genuine feature of the gel effect of this system under isothermal conditions. The propagation rate constant (kp) as a function of monomer conversion exhibited a marked dependence on initiator concentration at high monomer conversion; the sharp decrease in kp with increasing conversion was shifted to higher conversions with increasing initiator concentration.

A purple acid phosphatase from sweet potato contains an antiferromagnetically coupled binuclear Fe-Mn center

A purple acid phosphatase from sweet potato is the first reported example of a protein containing an enzymatically active binuclear Fe-Mn center. Multifield saturation magnetization data over a temperature range of 2 to 200 K indicates that this center is strongly antiferromagnetically coupled. Metal ion analysis shows an excess of iron over manganese. Low temperature EPR spectra reveal only resonances characteristic of high spin Fe(III) centers (Fe(III)-apo and Fe(III)-Zn(II)) and adventitious Cu(II) centers. There were no resonances from either Mn(II) or binuclear Fe-Mn centers. Together with a comparison of spectral properties and sequence homologies between known purple acid phosphatases, the enzymatic and spectroscopic data strongly indicate the presence of catalytic Fe(III)-Mn(II) centers in the active site of the sweet potato enzyme. Because of the strong antiferromagnetism it is likely that the metal ions in the sweet potato enzyme are linked via a mu -oxo bridge, in contrast to other known purple acid phosphatases in which a mu -hydroxo bridge is present. Differences in metal ion composition and bridging may affect substrate specificities leading to the biological function of different purple acid phosphatases.

Teleportation improvement by conditional measurements on the two-mode squeezed vacuum

We show that by making conditional measurements on the Einstein-Podolsky-Rosen (EPR) squeezed vacuum [T. Opatrny, G. Kurizki, and D.-G. Welsch, Phys. Rev. A 61, 032302 (2000)], one can improve the efficacy of teleportation for both the position-difference, momentum-sum, and number-difference, phase-sum continuous variable teleportation protocols. We investigate the relative abilities of the standard and conditional EPR states, and show that by conditioning we can improve the fidelity of teleportation of coherent states from below to above the (F) over bar =2/3 boundary, thereby achieving unambiguously quantum teleportation.

Synthesis and structural properties of patellamide a derivatives and their copper(II) compounds

The synthesis, characterization and copper(II) coordination chemistry of three new cyclic peptide ligands, PatJ(1) (cyclo-(Ile -Thr- (Gly)Thz-lle-Thr(Gly)Thz)), PatJ(2) (cyclo-(Ile-Thr(Gly)Thz-(D)-Ile-Thr-(Gly)Thz)), and PatL (cyclo-(Ile-Ser-(Gly)Thz-Ile-Ser(Gly)Thz)) are reported. All of these cyclic peptides and PatN (cyclo-(Ile-Ser(Gly)Thz-Ile-Thr-(Gly)Thz)) are derivatives of patellamide A and have a [24]azacrown-8 macrocyclic structure. All four synthetic cyclic peptides have two thiazole rings but, in contrast to patellamide A, no oxazoline rings. The molecular structure of PatJ1, determined by X-ray crystallography, has a saddle conformation with two close-to-co-parallel thiazole rings, very similar to the geometry of patellamide D. The two coordination sites of PatJ1 with thiazole-N and amide-N donors are each well preorganized for transition metal ion binding. The coordination of copper(II) was monitored by UV/Vis spectroscopy, and this reveals various (meta)stable mono- and dinuclear copper(II) complexes whose stoichiometry was confirmed by mass spectra. Two types of dinuclear copper(II) complexes, [Cu-2(H4L)(OH2)(n)](2+) (n = 6, 8) and [Cu-2(H4L)(OH2)(n)] (n=4, 6; L=PatN, PatL, PatJ1, PatJ2) have been identified and analyzed structurally by EPR spectroscopy and a combination of spectra simulations and molecular mechanics calculations (MM-EPR). The four structures are similar to each other and have a saddle conformation, that is, derived from the crystal structure of PatJ(1) by a twist of the two thiozole rings. The small but significant structural differences are characterized by the EPR simulations.