Evaluation of Monomer-containing Isocyanate Groups on Stabilizing Demineralized Dentin Matrix Against Bond Interface Degradation.

PURPOSE: To evaluate the effect of urethane methacrylate precursor (UMP) on the enzymatic resistance of demineralized dentin (DD) matrices. MATERIALS AND METHODS: Experimental treatments containing 0 (control), 1, and 5 mmol/L UMP dissolved in an acetone (Ace) solution were formulated. Dentin matrix specimens were demineralized in vitro and immersed in the experimental treatments for 1 h. The treated specimens were then stored in 0.1 mg/mL collagenase solution for 24 h, after which their dry mass loss and hydroxyproline (HYP) release were assessed. The swelling ratios of specimens in each group were also evaluated. The interaction between UMP and the dentin matrix was observed using field-emission scanning electron microscopy (FE-SEM). Endogenous enzyme activity in dentin was evaluated using confocal laser scanning microscopy (CLSM). RESULTS: Compared with the other treatment groups, treatment with 1 mM and 5 mM UMP-Ace significantly decreased the dry mass loss, HYP release and swelling ratio of the DD matrix (p < 0.05). FE-SEM and CLSM observations showed that treatment with UMP-Ace protected the structure of the dentin matrix and decreased porosity within the dentin-collagen network. CONCLUSION: Treatment with 1 mM and 5 mM UMP-Ace protects DD matrix against collagenase degradation and may be clinically useful for improving the durability of the hybrid layer.

In vitro comparison of bonding to zirconia- or glass- based ceramics between flowable resin composites and composite resin cements.

PURPOSE: To evaluate and compare the bonding of flowable resin composites and light-cured resin cements to dental ceramics. METHODS: Grit-blasted zirconia plates were primed with MDP-containing adhesive. Lithium disilicate glasses plates were etched with HF and primed with silane. Two flowable resin composites with high (CM: 75 wt%/62 vol%) and low (BF: 67.3 wt%/47 vol%) filler contents, and two resin cements, again with high (C: 72 wt%/69 vol%) and low (R: 66 wt%/47 vol%) filler contents, were bonded to both types of pretreated ceramics. Shear bond strength (SBS) was measured after 24 hours water storage or 10,000 times thermocycling between 5 and 55°C. The viscosities and film thicknesses of the four resin-based luting agents (RBLAs) were also explored by rotational rheometer and metallurgical microscope severally. RESULTS: Different RBLAs provided statistically different SBS values, with the high-filler specimens exhibiting higher SBS values than the low-filler specimens. The viscosities decreased in the order C > R > BF > CM. The film thicknesses for the BF and C groups were higher than those of the CM and R groups. CLINICAL SIGNIFICANCE: This study provides evidence that flowable resin composites with high filler contents and low viscosities may serve as an alternative to light-cured resin cements for luting zirconia or lithium disilicate glass. This expands the range of light-cured luting agents available for bonding of veneers or other thin restorations, which is of great benefit to clinical practice.

Effect of APTES- or MPTS-Conditioned Nanozirconia Fillers on Mechanical Properties of Bis-GMA-Based Resin Composites.

To investigate the effects of 3-aminopropyltriethoxysilane (APTES)- or (3-mercaptopropyl)trimethoxysilane (MPTS)-conditioned nanozirconia fillers on the mechanical properties of Bis-GMA-based resin composites. The conditioned fillers were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and thermodynamic calculations. They were then used to prepare Bis-GMA-based resin composites, whose flexural strength and elastic modulus were evaluated. The Cell Counting Kit-8 (CCK-8) assessed the composites' cytotoxicity. The FTIR spectra of the conditioned fillers showed new absorption bands at 1569 and 1100 cm-1, indicating successful grafting of APTES or MPTS onto nanozirconia. XPS confirmed the Zr-O-Si bonds in the APTES- or MPTS-conditioned fillers at contents of 2.02 and 6.98%, respectively. Thermodynamic calculations reaffirmed the chemical binding between the two silanes and nanozirconia fillers. Composites containing the conditioned nanozirconia fillers had significantly greater flexural strengths (APTES, 121.02 ± 8.31 MPa; MPTS, 132.80 ± 15.80 MPa; control, 94.84 ± 9.28 MPa) and elastic moduli (8.76 ± 0.52, 9.24 ± 0.60, and 7.44 ± 0.83 GPa, respectively) than a control with untreated fillers. The cytotoxicity assay identified no significant cytotoxicity by composites containing the conditioned fillers. Silanes were previously considered to be unable to chemically condition zirconia to bond with resin. Inclusion of APTES- or MPTS-conditioned nanozirconia fillers can improve the mechanical properties of Bis-GMA-based resin composites without obvious cytotoxicity in this study.

Mechanical Properties of Nanohybrid Resin Composites Containing Various Mass Fractions of Modified Zirconia Particles.

PURPOSE: The aim of this study was to investigate the effect of various mass fractions of 10-methacry-loyloxydecyl dihydrogen phosphate (MDP)-conditioned or unconditioned zirconia nano- or micro-particles with different initiator systems on the mechanical properties of nanohybrid resin composites. METHODS: Both light-cured (L) and dual-cured (D) resin composites were prepared. When the mass fraction of the nano- or micro-zirconia fillers reached 55 wt%, resin composites were equipped with dual-cured initiator systems. We measured the three-point bending-strength, elastic modulus, Weibull modulus and translucency parameter of the nanohybrid resin composites containing various mass fractions of MDP-conditioned or unconditioned zirconia nano- or micro-particles (0%, 5 wt%, 10 wt%, 20 wt%, 30 wt% and 55 wt%). A Cell Counting Kit (CCK)-8 was used to test the cell cytotoxicity of the experimental resin composites. The zirconia nano- or micro-particles with MDP-conditioning or not were characterized by transmission electron microscopy (TEM), Fourier infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). RESULTS: Resin composites containing 5-20 wt% MDP-conditioned or unconditioned nano-zirconia fillers exhibited better three-point bending-strength than the control group without zirconia fillers. Nano- or micro-zirconia fillers decreased the translucence of the nanohybrid resin composites. According to the cytotoxicity classification, all of the nano- or micro-zirconia fillers containing experimental resin composites were considered to have no significant cell cytotoxicity. The FTIR spectra of the conditioned nano- or micro-fillers showed new absorption bands at 1719 cm-1 and 1637 cm-1, indicating the successful combination of MDP and zirconia particles. The XPS analysis measured Zr-O-P peak area on MDP-conditioned nano- and micro-zirconia fillers at 39.91% and 34.89%, respectively. CONCLUSION: Nano-zirconia filler improved the mechanical properties of nanohybrid resin composites, but cannot be the main filler to replace silica filler. The experimental dual-cured composites can be resin cements with better opacity effects and a low viscosity.

Glycerol Phosphate Dimethacrylate: An Alternative Functional Phosphate Ester Monomer to 10-Methacryloyloxydecyl Dihydrogen Phosphate for Enamel Bonding.

The bonding performance of a glycerol phosphate dimethacrylate (GPDM)-based, two-step, self-etch (SE) adhesive was experimentally compared to that of 10-methacryloyloxydecyl dihydrogen phosphate (MDP)-based universal adhesives in different application modes for enamel bonding. Microtensile bond strength (µTBS) for adhesives bonded to enamel was measured initially (24 h water storage) and after 10 000 thermocycles plus water storage for 30 days. A GPDM-based, two-bottle, two-step, self-etch adhesive (Optibond Versa, OV) and three one-bottle MDP-based universal adhesives, one self-etching (Tetric N Bond Universal, TNBU) and two with etch-and-rinse (E&R) processing (Single Bond Universal (SBU); Clearfil Universal Bond Quick (CUBQ)), were tested. Scanning electron microscopy (SEM) evaluated nanoleakage at the bonding interfaces. A profilometer determined roughnesses of enamel surfaces after phosphoric acid etching, OV priming, or TNBU conditioning. SEM observed the corresponding surface morphology. NMR and X-ray photoelectron spectroscopy (XPS) characterized chemical bonding in hydroxyapatites (HAps) conditioned with the adhesives. Etch-and-rinse samples had significantly stronger bonding than self-etch samples (p < 0.05) irrespective of aging. The µTBS values for initial and aged OV were significantly higher than those of TNBU (p < 0.05). Aging did not significantly decrease µTBS for any sample except TNBU (p < 0.05), but it significantly aggravated nanoleakage. Etch-and-rinse processing resulted in less nanoleakage than self-etching; the OV samples leaked less than TNBU, both before and after aging. Phosphoric acid etching achieved the highest enamel surface roughness, followed by OV primer. Ca-O-P bonds in hydroxyapatite conditioned with TNBU, SBU, and CUBQ were confirmed by NMR, which showed similar results to XPS observations of conditioned hydroxyapatite powders except OV primer. The GPDM-based, two-step, self-etch adhesive can provide higher micromechanical retention potential, bond strength, and durability than the MDP-based universal adhesive in self-etch mode but lower performance than the MDP-based universal adhesive in etch-and-rinse mode. None of the tested adhesives could avoid nanoleakage after aging.

Modulation of Symbiotic Compatibility by Rhizobial Zinc Starvation Machinery.

Pathogenic bacteria need high-affinity zinc uptake systems to counteract the nutritional immunity exerted by infected hosts. However, our understanding of zinc homeostasis in mutualistic systems such as the rhizobium-legume symbiosis is limited. Here, we show that the conserved high-affinity zinc transporter ZnuABC and accessory transporter proteins (Zip1, Zip2, and c06450) made cumulative contributions to nodulation of the broad-host-range strain Sinorhizobium fredii CCBAU45436. Zur acted as a zinc-dependent repressor for the znuC-znuB-zur operon, znuA, and c06450 by binding to the associated Zur box, but did not regulate zip1 and zip2 ZnuABC was the major zinc transporter. Combined mutants lacking znuA and one of the three accessory genes had more severe defects in nodulation and growth under zinc starvation conditions than the znuA mutant, though rhizoplane colonization by these mutants was not impaired. In contrast to the elite strain CCBAU45436, more drastic symbiotic defects were observed for the znuA mutants of other Sinorhizobium strains, which lack at least one of the three accessory genes in their genomes and are characterized by their limited host range and geographical distribution. The znu-derived mutants showed a higher expression level of nod genes involved in Nod factor biosynthesis and a reduced expression of genes encoding a type three secretion system and its effector NopP, which can interfere with the host immune system. Application of exogenous zinc restored the nodulation ability of these znu-derived mutants. Therefore, the conserved ZnuABC and accessory components in the zinc starvation machinery play an important role in modulating symbiotic compatibility.IMPORTANCE The rhizobium-legume symbiosis contributes around 65% of biological nitrogen fixation in agriculture systems and is critical for sustainable agriculture by reducing the amount of chemical nitrogen fertilizer being used. Rhizobial inocula have been commercialized for more than 100 years, but the efficiency of inoculation can vary among legume cultivars, field sites, and years. These long-lasting challenging problems impede the establishment of a sustainable agriculture, particularly in developing countries. Here, we report that rhizobial zinc starvation machinery containing a conserved high-affinity zinc transporter and accessory components makes cumulative contributions to modulating rhizobial symbiotic compatibility. This work highlights a critical role of largely unexplored nutritional immunity in the rhizobium-legume symbiosis, which makes zinc starvation machinery an attractive target for improving rhizobial symbiotic compatibility.

Choice of resin cement shades for a high-translucency zirconia product to mask dark, discolored or metal substrates.

PURPOSE: The aim was to study the masking ability of high-translucency monolithic zirconia and provide guidance in selecting resin luting cements in order to mask discolored substrates. MATERIALS AND METHODS: 160 high-translucency zirconia specimens were divided into 32 groups depending on their thickness and shades. Using five shades of try-in paste, the specimens were luted onto the sub strates (Co-Cr, precious-metal, opaque porcelain-sintered Co-Cr, opaque porcelain-sintered precious-metal, and 5M3-shade zirconia). All CIELAB color parameters were measured and statistically analyzed. RESULTS: Zirconia shade and thickness and try-in paste shade affected CIELAB color parameters (P=.000) in different substrates groups, and there were interactions among these factors (P=.000). All five try-in paste shades can be chosen to achieve ΔE values of zirconia with 1.2 - 1.5 mm for masking dark-tooth-like 5M3-shade and zirconia with 1.5 mm for masking precious-metal groups < 2.6. Only suitable try-in paste shades were used, can ΔE values that less than 2.6 be achieved when applied translucent monolithic zirconia with 0.7-1.0 mm for masking dark-tooth-like 5M3-shade and zirconia with 0.7 - 1.2 mm for masking precious-metal groups. CONCLUSION: Choosing suitable resin cement shades is necessary for high-translucency monolithic zirconia to achieve ideal masking ability (ΔE < 2.6) on the dark-tooth.

Reinforcement of dental resin composite via zirconium hydroxide coating and phosphate ester monomer conditioning of nano-zirconia fillers.

OBJECTIVES: The present study aimed to evaluate effects of conditioning with the phosphate ester monomer 10-methacryloyloxydecyl dihydrogen phosphate (MDP), with and without precoating with zirconium hydroxide for nano-size zirconia fillers, on mechanical properties of dental resin composites. MATERIALS AND METHODS: Nano-zirconia fillers coated with or without zirconium hydroxide [Zr(OH)4] were prepared. Transmission electron microscopy (TEM), Fourier infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) were used to observe the coating and to characterize Zr(OH)4 coating on the zirconia filler surface. Zirconia fillers with or without Zr(OH)4 coating were conditioned with MDP and were subsequently used to prepare experimental resin composites. XPS was used to analyze the Zr-O-P bonds on the filler surface after MDP conditioning. Moreover, three-point bending strength and elastic modulus of prepared resin composites were measured, and Weibull analysis was performed. Resin composites without addition of zirconia fillers and the ones with addition of untreated or silane conditioned-zirconia fillers were set as controls. Cell counting kit (CCK)-8 was used to test cell cytotoxicity of these zirconia fillers-containing experimental resin composites. RESULTS: Nano-zirconia fillers were coated with Zr(OH)4 through chemical deposition. FTIR and XPS analysis confirmed the increase of hydroxyl groups after Zr(OH)4 coating. XPS detected the highest contents of Zr-O-P bonds on MDP-conditioned zirconia fillers with pre-Zr(OH)4 coating, followed by MDP-conditioned zirconia fillers. Resin composite with added MDP-conditioned zirconia fillers with and without Zr(OH)4 coating exhibited greater three-point bending strength, elastic modulus values, and Weibull moduli. According to the cytotoxicity classification, resin composites containing experimental zirconia fillers were considered to have no significant cell cytotoxicity. CONCLUSION: Nano-zirconia fillers conditioned with MDP, with or without precoating with Zr(OH)4, improve the mechanical properties of resin composites, and are potentially safe for clinical use.

Surface Treatment Of Nanozirconia Fillers To Strengthen Dental Bisphenol A-Glycidyl Methacrylate-Based Resin Composites.

PURPOSE: To investigate the effects of nanozirconia fillers conditioned with 10-methacryloyloxydecyl dihydrogen phosphate (MDP) with or without zirconium hydroxide precoating on bending strength, Vickers hardness, and translucence of dental resin composites. METHODS: We obtained nanozirconia fillers coated with different concentrations of Zr(OH)4 using wet-chemical synthesis. We analyzed coating quality by observing electron-diffraction patterns using transmission electron microscopy. We conditioned zirconia fillers, with or without prior Zr(OH)4-coating, using MDP-containing primers and evaluated the formation of chemical bonds using nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS). We then performed three-point bending-strength tests, Weibull analysis, Vickers hardness, and translucence-parameter analysis with or without addition of different concentrations of zirconia using untreated zirconia fillers as controls. RESULTS: We achieved desirable Zr(OH)4 coating using 5 mmol/L zirconium chloride. NMR and XPS analysis detected stronger Zr-O-P peaks on MDP-conditioned zirconia fillers with prior Zr(OH)4-coating compared with MDP-conditioned fillers alone, suggesting that MDP bonding with zirconia was enhanced by zirconium hydroxide. Our three-point bending-strength tests revealed that increasing levels of untreated zirconia fillers decreased the three-point bending strength of the resin composites, while MDP-conditioned zirconia fillers with or without prior Zr(OH)4 coating improved three-point bending strengths. Adding 5 wt% and 7.5 wt% MDP-conditioned zirconia fillers with prior Zr(OH)4 coating achieved the highest three-point bending strength. Furthermore, addition of zirconia fillers decreased the translucence of silica-based resin composites. CONCLUSION: MDP conditioning with prior Zr(OH)4 coating is recommended for treating nanozirconia fillers of resin composites.

Enhanced performance of polyimide hybrid membranes for benzene separation by incorporating three-dimensional silver-graphene oxide.

Graphene oxide-Ag nanoparticle composites were prepared through impregnation reduction using different reactants. Transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy analyses were performed to characterize differences in the morphologies of three different Ag-GO composites. Scanning electron microscopy, transmission electron microscopy, and differential scanning calorimetry analyses were also applied to evaluate the morphology and thermal stability of the hybrid membranes. Swelling-sorption and pervaporation experiments of benzene and cyclohexane were conducted to evaluate the separation performance of hybrid membranes containing different Ag-GO composites. Results demonstrated that small Ag nanoparticles generated through impregnation reduction using Ag(NH3)2(+) and PEG were homogeneously distributed in the hybrid membranes because of moderate reduction rate. The polymide (PI) hybrid membrane exhibited high separation performance. Increase in Ag content in the Ag-GO samples led to the formation of Ag particles on the GO surface; these particles enhanced the separation performance of the hybrid membranes. When Ag-GO samples with 15 mass percent added, the hybrid membrane showed the highest separation performance and its maximum separation factor in the pervaporation experiments reached 35. It is more than three times higher than that of the GO/PI hybrid membrane. Moreover, large Ag particles were formed and aggregated during the preparation and polymerization of Ag-GO samples with high Ag contents; these particles reduced the separation performance of the hybrid membranes.