Effects of Different Silane Coupling Agent Monomers on Flexural Strength of an Experimental Filled Resin Composite

The hydrolytic stability of various silane combinations and their effects on biomechanical properties and water sorption of an experimental dental composite made of bis-GMA and TEGDMA and silane-treated fillers were evaluated. Four silane coupling agents and their blends with a cross-linker silane were used as coupling agents for the 0.7-μm BaSiO₃ fillers. The silanization was carried out in toluene containing 1% (v/v) of one of the four following organofunctional silane coupling agents: 3-acryloxypropyltrimethoxysilane, 3methacryloxypropyltrimethoxysilane, 3-styrylethyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane. Blends of these functional silanes with 1% (v/v) of a cross-linker silane, 1,2- bis -(triethoxysilyl)ethane were also used for silanization. Composites were prepared by mixing 5.00 g Ba-glass filler with 2.00 g of a resin mixture consisting of bis-GMA (58.8 wt%) and TEGDMA (39.2 wt%) in a high-speed mixer. Threepoint bending test specimens (2.0 mm × 2.0 mm × 25.0 mm) were fabricated (n= 8) in a mould and photo-polymerized. The degree of conversion was measured with FT-IR. Biomechanical testing was carried out according to the ISO 10477 standard. Specimens were tested (flexural strength) after 30 days of water storage (37° C, distilled water). Water sorption and solubility (in wt%) were also measured on 1, 2, 3, 5, 7, 14, 21 and 30 days in water storage. Statistical analysis with ANOVA showed that the highest flexural strength was obtained when 3-acryloxypropyltrimethoxysilane + 1,2- bis -(triethoxysilyl)ethane (100.5 MPa; SD, 25.7 MPa) was used in the silanization step, and the lowest was obtained when 3isocyanatopropyltriethoxysilane + 1,2- bis-(triethoxysilyl)ethane (28.9 MPa; SD, 8.8 MPa) was used. The three-point bending strength was significantly affected by the functionality of the main silane tested (p< 0.05), but not by the addition of the cross-linker silane ( p> 0.05). The composite that had been silanized with 3-isocyanatopropyltriethoxysilane had the greatest amount of water uptake (1.75%), and the composite silanized with 3-methacryloxypropyltrimethoxysilane + 1,2- bis-(triethoxysilyl)ethane had the least (1.08%). In conclusion, selection of the functional silane monomer can be a significant factor in developing filled resin composites in dentistry.     

Influence of Surface Nano-roughness of Dental Alumina Ceramic on Bond Strength to Dual-Cure Resin Cements

The goal of this research is to evaluate the effect of sandblasting and silica coating on the nano-roughness and on the microtensile bond strength (MTBS) of glass-infiltrated alumina bonded to different resin cements. Six slabs of In-Ceram Alumina (Vita) were randomly treated according to the following groups: (1) no treatment; (2) sandblasting (125 μm Al₂O₃-particles); and (3) tribochemical silica-coating (50 μm silanated silica particles). Nano-roughness (Ra) was assessed under an atomic force microscope (AFM). Such surface treatments were also applied to nine In-Ceram Alumina CAD/CAM blocks. Ceramic blocks were duplicated in composite resin, and composite samples were bonded to the conditioned surfaces. Each pre-treatment group was divided into three subgroups depending on the resin cement system: (1) Clearfil Ceramic Primer plus Clearfil Esthetic Cement (CEC, Kuraray); (2) RelyX Unicem (RXU, 3M); and (3) Calibra Silane plus Calibra Resin Cement (CAL, Dentsply). After 24 h, the bonded specimens were cut into 1±0.2 mm² sticks. The MTBS values (MPa) were obtained using a universal testing machine (crosshead speed: 0.5 mm/min). Failure modes were recorded using a scanning electron microscope (SEM). Nano-roughness and MTBS data were analyzed by ANOVA and Student–Newman–Keuls tests (α =0.05). No significant changes in nano-roughness occurred after conditioning. The MTBS of CEC and RXU were comparable despite the surface treatment. All CAL-sticks debonded prematurely. Ceramic pre-treatments, such as sandblasting or silica coating, do not affect the alumina's surface nano-roughness or bond strength. The MDP monomers dissolved in the CEC Primer and the functional dimethacrylate monomers present in the self-adhesive RXU may be the key to successful bonds to alumina.     

Combined Novel Bonding Method of Resin to Zirconia Ceramic in Dentistry: A Pilot Study

Zirconia is a promising metal-free framework material that can be used to construct all-ceramic resin-bonded restorations in modern minimally invasive dentistry. The lack of a durable bond to zirconia is the major limitation against its widespread use. A technique to promote adhesion to the zirconia surface has thus been actively sought in dental materials research. Selective infiltration etching (SIE) has emerged as a method of conditioning that creates a highly retentive zirconia surface. This in vitro pilot study tested a novel adhesion procedure in which two newly engineered silane-based zirconia primers were combined with the SIE method. Zirconia discs were SIE-surface-treated, coated with one of the 2 zirconia primers, and bonded to composite resin discs. Primer activation (hydrolysis) was monitored by Fourier transform infrared (FTIR) spectroscopy. The bilayered specimens were sectioned into microbars and subjected to the microtensile bond strength test. As-sintered zirconia discs served as controls. Surface analysis of zirconia specimens was carried out using photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Zirconia specimens that had been treated with both SIE and primers had a significantly higher (ANOVA) zirconia resin bond strength (40.6 MPa, SD 5.8 MPa) than control specimens (2.6 MPa, SD 3.0 MPa; p < 0.05, F = 13.8, ANOVA). Controls also exhibited spontaneous failure during sectioning. Additionally, the interfacial failure rate was lower for the specimens subjected to the new combined surface treatment than for controls. The novel combined method of surface treatment method might open new opportunities for enhanced adhesion of resin-bonded zirconia restorations.     

Heterogeneity in the strength of interfacial bonds and the resultant synergism in promoting polyurethane/SBR adhesion strength

Polymer adhesion and its evaluation are very important both from academic and industrial points of view. Adhesion phenomenon depends mainly on the strength of interfacial bonds and the deformability of adhering partners, which act as another energy absorbing term. Using a combination of acid-base interactions and a coupling agent at the interface of styrene-butadiene (SBR)-polyurethane system, a synergistic adhesion promotion was observed. The SBR surface was treated with an acidified aqueous solution of calcium hypochlorite to obtain polar groups, which can interact with the isocyanate groups of the polyurethane system. Aminopropyltriethoxysilane, a coupling agent, was also deposited at the SBR surface, after treating it with the aforementioned solution. The polar groups on the SBR apparently interact with the OH sites of the coupling agent at the surface and push the amino groups toward the polyurethane surface. This interesting finding, synergistic adhesion promotion, was attributed to the tortuous path for the crack growth at the interface, which was created by formation of the interfacial bonds with different strengths (heterogeneous bond strength). Furthermore, to obtain the highest synergistic effect, it seems that certain ratio of bonds with different strengths should be formed. The ratio itself depends on the deformability ratio of the adhering materials.     

Effect of the Etching Duration and Ultrasonic Cleaning on Microtensile Bond Strength Between Feldspathic Ceramic and Resin Cement

This study assessed the effect of different etching durations of feldspathic ceramic with hydrofluoric acid (HF) and ultrasonic cleaning of the etched ceramic surface on the microtensile bond strength stability of resin to a feldspathic ceramic. The research hypotheses investigated were: (1) different etching times would not affect the adhesion resistance and (2) ultrasonic cleaning would improve the adhesion. Ceramic blocks (6 × 6 × 5 mm) (N = 48) were obtained. The cementations surfaces were duplicated in resin composite. The six study groups (n = 8) were: G1—Etching with 10% aqueous HF (30 s) + silane; G2—10% HF (1 min) + silane; G3—10% HF (2 min) + silane; G4—10% HF (30 s) + ultrasonic cleaning (4 min) in distilled water +silane; G5—10% HF (1 min) + ultrasonic cleaning + silane; G6—10% HF (2 min) ultrasonic cleaning + silane. The cemented blocks were sectioned into microbars for the microtensile test. The etching duration did not create significant difference among the groups (p = .156) but significant influence of ultrasonic cleaning was observed (p = .001) (Two-way ANOVA and Tukey's test, p > 0.05). All the groups after ultrasonic cleaning presented higher bond strength (19.38–20.08 MPa) when compared with the groups without ultrasonic cleaning (16.21–17.75 MPa). The bond strength between feldspathic ceramic and resin cement was not affected by different etching durations using HF. Ultrasonic cleaning increased the bond strength between ceramic surface and resin cement, regardless of the etching duration.     

Short Exposure to 1% Hydrofluoric Acid to Improve the Repair Bond Strength of Dental Resin Composites

Application of 1% hydrofluoric acid (HFA) to improve the repair bond strength of a microhybrid (Z250; 3 M/ESPE) and a nanofilled dental composite (Supreme XT, 3 M/ESPE) was investigated. Aged composites were etched using 1% HFA for 10, 30, or 60 s. Negative (non-etched) and positive (10% HFA for 60 s) control groups were tested. The surfaces received a layer of a silane and adhesive (Single Bond 2; 3 M/ESPE). Cylinders of fresh composite (n = 15 per group) were built up and a shear bond strength test was carried out after water storage for 24 hr or 6 months. Surface topography was assessed using atomic force microscopy (AFM). For the nanofill at 24 hr, all etching regimens yielded higher bond strengths than the negative control. After 6 months, the negative and positive controls showed lower bond strength than 1% HFA for 30 s. For the microhybrid, the negative control generally showed lower bond strength at 24 hr, while all groups had similar results after 6 months. Only the positive controls showed lower bond strengths after 6 months. AFM analysis showed that the nanofill was more susceptible to acid-etch roughening. In conclusion, exposure to 1% HFA may improve the repair bond strength of dental composites.     

The prediction of adhesion between polymer matrices and silane-treated glass surfaces in filled composites

Extending the database and the analysis of work reported earlier, the practical adhesion between a glass filler, modified by various silane coupling agents, and different polymeric matrices is measured and compared with predictions based on a generalized thermodynamic criterion. The criterion used is the magnitude of the (negative) molar Gibbs free energy of mixing, (-ΔGmix)_0.5, for a pseudo-solution consisting of equal molar amounts of the repeat units of the polymer matrix and the organo-functional group of the silane coupling agent. It is computed using the group contribution method of UNIFAC, in which molar volumes, molar areas, and molar interaction energies are constructed from contributions of the functional groups which make up the molecules of the solution. Measurements leading to the values of the adhesion strength are carried out using the singleparticle composite method, in which a rectangular polymer specimen containing a single silane-treated glass bead is subjected to increasing uni-axial tensile stress until interfacial failure, as observed using a microscope, occurs at one of the poles of the sphere. Earlier work reported a good correlation between the local stress at the pole computed from such measurements and the value of (-ΔG _mix)_0.5 computed using UNIFAC for ten different organo-silane-modified spheres imbedded in a poly(vinyl butyral) matrix. The present work extends the database to two additional matrices, viz. poly(methyl methacrylate) and poly(ethyl methacrylate). In addition, elastic fracture-mechanics theory is used to deduce specific adhesion energies in all cases. The relative values of the latter are all found to be in good correlation with the predictive thermodynamic criterion.     

潮湿环境对树脂基复合材料制品生产的影响分析

本文针对复合材料制品在特定环境下成型过程中出现的固化不完全问题，分析了问题产生的原因，并给出了树脂基复合材料制品在潮湿环境中生产应注意的事项和方法。     

内压容器筒体与大接管相贯区的应力强度评定

针对内压容器筒体开有大直径孔后会产生很高的应力集中这一问题,采用有限元方法计算了具有同一开孔率但有不同接管与筒体直径比的压力容器结构的应力分布,并在应力危险截面选择了5条应力处理线进行了应力强度评定。结果发现,5条应力处理线中处理线c的一次局部薄膜应力分量SⅡ最大;而一次应力加二次应力SⅣ的最大值则随t/T的大小体现在不同的处理线上,故SⅣ的评定应针对各处理线进行。在笔者的算例中,4种t/T结构中只有t/T=1.0的结构可满足应力分析设计准则要求。     

离子强度和富里酸对纳米 TiO2在土壤中迁移的影响

采用自然土壤作为介质,研究了离子强度、富里酸对纳米TiO2在土壤中迁移性能的影响。结果表明,随着离子强度从0 mM增加至0．5 mM和5 mM,纳米TiO2在土壤中的相对流出浓度（ C／C0）从0．85分别降低为0．45和0。然而,体系中含有富里酸时,纳米TiO2在土壤中的迁移能力变强了,5 mg／L和10 mg／L的富里酸分别使nTiO2的相对流出浓度提高到0．89和0．95,大大增加其环境风险。     

容器支座区域局部应力的有限元计算和强度评定

运用有限元法对工业中的大型搅拌反应器悬挂式支座处应力进行了计算,得到了应力分布场,并采用应力分类的分析设计原理,对反应器的局部应力进行了强度评定。分析结果表明,该反应器支座区域的强度足够,可满足安全要求。     

The Effect of Surface Preparation and Exposure Environment on the Bond Failure Processes in Adhesively Bonded Sheet Molded Composite (SMC)

The durability of adhesively-bonded composites has been investigated using a wedge-type specimen. Polyester-resin, fiberglass sheet molded composite (SMC) was bonded with a commercial two-part poly-urethane adhesive. The SMC composite received one of four different surface preparations: no treatment, abrasion, priming, or abrasion and priming. The wedge test was used to study the durability of the samples which were exposed to air and to the vapor above water, concentrated ammonium hydroxide, or methanol at 60[ddot]C. The crack length was measured during the experiments. The crack growth rate as a function of surface treatment varied in the manner: untreated ≈ abraded > primed ≈ abraded and primed. The crack growth rate as a function of vapor changed in the manner: methanol > ammonium hydroxide > water ≈ air. The samples were removed at the conclusion of the test and the failure mode was determined visually, by scanning electron microscopy (SEM), and by X-ray photoelectron spectros-copy (XPS). Initial insertion of the wedge resulted in substrate failure (delamination of the composite). Exposure of untreated and abraded samples under stress to the test vapors promoted adhesive failure. Primed and abraded/primed samples under stress and exposed to methanol vapor debonded via cohesive processes.     

Evaluation of the Interaction between Bax and Hsp70 in Cells by Using a FRET System Consisting of a Fluorescent Amino Acid and YFP as a FRET Pair

To gain insight into factors that lead to dissociation of Bax from a complex with Hsp70 during apoptosis, we recently constructed a fluorescence resonance energy transfer (FRET) system composed of the Hsp70-YFP (YFP=yellow fluorescent protein) fusion protein and fluorescent amino acid (ANAP=6-acetyl(naphthalen-2-ylamino)-2-aminopropanoic acid)-containing Bax (Bax-ANAP), which was produced by using the genetic code expansion technique. In the current study, the FRET system was employed to elucidate how brefeldin A (an endoplasmic reticulum stress inducer), chlorpromazine and apoptozole (lysosomal membrane destabilizers), bafilomycin A1 (an inhibitor of lysosomal acidification) as well as raptinal and Az-TPP-O3 (mitochondria-targeted apoptosis inducers) affect the interaction between Bax and Hsp70. Analyses of single live cell images together with results of co-immunoprecipitation assays reveal that brefeldin A, chlorpromazine, and apoptozole promote dissociation of the Bax/Hsp70 complex through activation of the activator BH3-only protein. However, the results show that bafilomycin A1, raptinal, and Az-TPP-O3 have no influence on the interaction of Bax with Hsp70. The combined observations made in the current and previous studies demonstrate that the FRET system consisting of Bax-ANAP and Hsp70-YFP is highly useful to understand apoptotic processes associated with the Bax–Hsp70 interaction.     

Effect of the Cobalt Ion and Polyethyleneimine Adsorption on the Surface Forces between Tungsten Oxide and Cobalt Oxide in Aqueous Media

We used the colloidal probe technique with atomic force microscopy to study the interactions between a tungsten oxide sphere, WO₃, and flat oxidized tungsten and cobalt surfaces in aqueous electrolytes. We investigated the effects of adsorption of cobalt ions to tungsten oxide surfaces and adsorption of polyethyleneimine (PEI). Low concentrations of cobalt ions added to a WO₃ system resulted in extended hydration forces and a lowering of the absolute value of the surface potential. PEI was shown to adsorb to the WO₃ surfaces and induce an electrosteric repulsion in both the symmetric (WO₃–WO₃) and asymmetric (WO₃–CoOOH) systems. The possible complexation of cobalt ions with PEI does not significantly influence the thickness of the adsorbed layer.     

In Vitro Investigation of Crosstalk between Fatty Acid and Polyketide Synthases in the Andrimid Biosynthetic Assembly Line

Andrimid (Adm) synthase, which belongs to the type II system of enzymes, produces Adm in Pantoea agglomerans. The adm biosynthetic gene cluster lacks canonical acyltransferases (ATs) to load the malonyl group to acyl carrier proteins (ACPs), thus suggesting that a malonyl‐CoA ACP transacylase (MCAT) from the fatty acid synthase (FAS) complex provides the essential AT activity in Adm biosynthesis. Here we report that an MCAT is essential for catalysis of the transacylation of malonate from malonyl‐CoA to AdmA polyketide synthase (PKS) ACP in vitro. Catalytic self‐malonylation of AdmA (PKS ACP) was not observed in reactions without MCAT, although many type II PKS ACPs are capable of catalyzing self‐acylation. This lack of self‐malonylation was explained by amino acid sequence analysis of the AdmA PKS ACP and the type II PKS ACPs. The results show that MCAT from the organism's FAS complex can provide the missing AT activity in trans, thus suggesting a protein–protein interaction between the fatty acid and polyketide synthases in the Adm assembly line.     

Third Phase Formation in the Extraction of Th(NO3)4 by Tri-n-Butyl Phosphate and Tri-iso-Amyl Phosphate in n-Dodecane and n-Tetradecane from Nitric Acid Media

Binary solutions of tri-n-butyl phosphate (TBP) or tri-iso-amyl phosphate (TiAP) in n-dodecane or n-tetradecane (1.1 M) as diluents have been investigated for third phase formation in the extraction of Th(NO₃)₄ from its solutions with 1 M or 5 M HNO₃ as a function of equilibrium aqueous phase Th(IV) concentration ([Th(IV)]_aq,eq) at 303 K. Extraction isotherms for the extraction of Th(IV) and HNO₃ have been generated with respect to [Th(IV)]_aq,eq. The difference in density between the third phase and the diluent-rich phase as well as the diluent-rich phase and the pure diluent, ratio of volume of the diluent-rich phase to that of the third phase have also been determined over a wide range of [Th(IV)]_aq,eq in the triphasic region. An attempt has also been made to determine the extractant concentrations in the third phase and the diluent-rich phase in the extraction of Th(NO₃)₄ by the above solvents from its saturated solutions with 1 M and 5 M HNO₃.     

翻盘过滤机与转台过滤机在湿法磷酸生产中的应用比较

翻盘过滤机与转台过滤机的构造有许多共同点，但在过滤洗涤操作中的运行情况和效果却有不同，针对这两种过滤机在湿法磷酸生产中的运用进行比较，以便对生产装置的扩能改造提供一些参考依据。     

Evaluation of the Correlation between Porphyrin Accumulation in Cancer Cells and Functional Porphyrin Positions of the Phenyl Group

Porphyrin selectively shows tumour accumulation and has attracted attention as a carrier molecule for drug delivery systems (DDS). Porphyrin has two functional sites termed the meso- and β-positions. In previous work, meso-porphyrin derivatives with an alkyl group were found to exhibit greater accumulation in human breast cancer cells (MCF-7). To identify the correlation between porphyrin accumulation and functional porphyrin positions of other functional groups, the accumulation of porphyrin derivatives with a phenyl group was investigated. The β-porphyrin derivative with a phenyl group showed higher accumulation in MCF-7 cells and greater affinity for albumin than the meso-porphyrin derivative. The results of density functional theory (DFT) calculations suggest that the β-porphyrin derivative with a phenyl group had higher planarity across the total structure than the meso-porphyrin derivative. It was concluded that the greater planarity of the β-porphyrin derivative with a phenyl group might lead to superior MCF-7 cell accumulation.     

Vaccenic Acid and <Emphasis Type="Italic">cis</Emphasis>-9,<Emphasis Type="Italic">trans</Emphasis>-11 CLA in the Rumen and Different Tissues of Pasture- and Concentrate-Fed Beef Cattle

The objective of present study was the comparison of trans-11 18:1 (VA) and cis-9,trans-11 CLA concentrations in the rumen and different tissues in beef cattle, and to examine the diet and breed effects on the compound concentration and deposition. Sixty-four German Holstein and German Simmental bulls were randomly assigned to two dietary treatments, based on concentrate or pasture. The concentration of cis-9,trans-11 CLA and VA in rumen, duodenal digesta and different tissues was determined by gas chromatography. The results showed that pasture relative to concentrate feeding significantly increased the concentration of VA in duodenal digesta, plasma and erythrocyte phospholipids. Pasture-based feeding resulted in a significant enrichment of cis-9,trans-11 CLA in plasma lipids and erythrocyte phospholipids, but not in rumen and duodenal digesta, compared to concentrate-fed diet. Diet did not affect the cis-9,trans-11 CLA concentrations (mg/100 g fresh tissue) in semitendinosus muscle and subcutaneous fat. There was a breed effect on the deposition of cis-9,trans-11 CLA in longissimus muscle with lower concentration in pasture-fed German Simmental bulls compared to concentrate-fed bulls. However, pasture feeding significantly increased both, the VA and cis-9,trans-11 CLA concentrations in liver and heart tissues. Both diet and breed effects on Δ⁹-desaturase index was observed in muscle and subcutaneous fat tissues. There was a linear relationship between the concentration of VA and cis-9,trans-11 CLA and the coefficients of determination (R ²) varied between 0.29 and 0.87 from rumen to the different tissues.