Hybrid layer-by-layer assembly based on animal and vegetable structural materials: multilayered films of collagen and cellulose nanowhiskers

Layer-by-layer (LBL) assembly was used to combine crystalline rod-like nanoparticles obtained from a vegetable source, cellulose nanowhiskers (CNWs), with collagen, the main component of skin and connective tissue found exclusively in animals. The film growth of the multilayered collagen/CNW was monitored by UV-Vis spectroscopy and ellipsometry measurements, whereas the film morphology and surface roughness were characterized by SEM and AFM. UV-Vis spectra showed the deposition of the same amount of collagen, 5 mg m(-2), in each dipping cycle. Ellipsometry data showed an increment in thickness with the number of layers, and the average thickness of each bilayer was found to be 8.6 nm. The multilayered bio-based nanocomposites were formed by single layers of densely packed CNWs adsorbed on top of each thin collagen layer where the hydrogen bonding between collagen amide groups and OH groups of the CNWs plays a mandatory role in the build-up of the thin films. The approach used in this work represents a potential strategy to mimic the characteristics of natural extracellular matrix (ECM) which can be used for applications in the biomedical field.

Effects of Nd:YAG Laser Irradiation on the Hybrid Layer of Different Adhesive Systems

Purpose: The aim of this in vitro study was to evaluate the microtensile bond strength (mu TBS) and hybrid layer morphology of different adhesive systems, either followed by treatment with Nd:YAG laser irradiation or not. Previous studies have shown the effects of Nd:YAG laser irradiation on the dentin surface at restoration margins, but there are few reports about the significance of the irradiation on the hybrid layer. Materials and Methods: The flattened coronal and root dentin samples of 24 bovine teeth were randomly divided into 8 groups, according to the adhesive system used - Scotchbond Multi Purpose (SBMP) or Clearfil SE Bond (CSEB) - and were either irradiated with Nd:YAG or not, with different parameters: 0.8 W/10 Hz, 0.8 W/20 Hz, 1.2 W/10 Hz, 1.2 W/20 Hz. The left sides of specimens were the control groups, and right sides were irradiated. A composite crown was built over bonded surfaces and stored in water (24 h at 37 degrees C). Specimens were sectioned vertically into slabs that were subjected to mu TBS testing and observed by SEM. Results: Control groups (27.81 +/- 1.38) showed statistically higher values than lased groups (21.37 +/- 0.99), and CSEB control group values (31.26 +/- 15.71) were statistically higher than those of SBMP (24.3 +/- 10.66). There were no significant differences between CSEB (20.34 +/- 10.01) and SBMP (22.43 +/- 9.82) lased groups. Among parameters tested, 0.8 W/10 Hz showed the highest value (25.54 +/- 11.74). Nd:YAG laser irradiation caused dentin to melt under the adhesive layer of both adhesive systems tested. Conclusion: With the parameters used in this study, Nd:YAG laser irradiation of the hybrid layer promoted morphological changes in dentin and negatively influenced the bond strength of both adhesive systems.

Flexible organic–inorganic hybrid layer encapsulation for organic opto-electronic devices

In this work we produce and study the flexible organic–inorganic hybrid moisture barrier layers for the protection of air sensitive organic opto-electronic devices. The inorganic amorphous silicon nitride layer (SiNx:H) and the organic PMMA [poly (methyl methacrylate)] layer are deposited alternatingly by using hot wire chemical vapor deposition (HW-CVD) and spin-coating techniques, respectively. The effect of organic–inorganic hybrid interfaces is analyzed for increasing number of interfaces. We produce highly transparent (∼80% in the visible region) hybrid structures. The morphological properties are analysed providing a good basis for understanding the variation of the water vapor transmission rate (WVTR) values. A minimum WVTR of 4.5 × 10−5g/m2day is reported at the ambient atmospheric conditions for 7 organic/inorganic interfaces. The hybrid barriers show superb mechanical flexibility which confirms their high potential for flexible applications.

Hybrid layer thickness and resin tag length of a self-etching adhesive bonded to sound dentin

Objectives: the purpose of this study is to employ optical microscopy to measure the thickness of the hybrid layer and the penetration (tags) of an aggressive self-etching adhesive system into sound dentin.Methods: occtusat cavities were prepared in 40 extracted human posterior teeth. The prepared teeth were randomly assigned to four experimental groups with 10 specimens each. The self-etching adhesive system Adper Prompt L-Pop was applied to the dentin surface as follows: Group 1: cavosurface enamel was etched for 60 s and dentin for 20 s with 35% phosphoric acid get, immediately followed by application of the self -etching adhesive with a brush to the entire cavity for 15 s; Groups 2, 3, and 4: no pre-etching was performed, and the self -etching adhesive was applied to both enamel and dentin for 15, 30 and 45 s, respectively. After curing, the cavities were fitted with composite resin Fittek Z250. Afterwards, the teeth were decalcified and the restorations were carefully removed for later embedding in paraffin. The specimens were serially sectioned at 6 mu m of thickness and sequentially mounted in glass slides. These sections were stained with Brown and Brenn staining for posterior analysis and measurement of the hybrid layer and resin tags on a tight microscope with a micrometric ocular 40/075. The results were submitted to analysis of variance at the 5% level.Results: whenever there was significance, the Tukey test was applied at the 5% level. The specimens receiving application of acid etching before the selfetching. adhesive displayed a larger thickness of the hybrid layer; on the other hand, specimens receiving only application of the self -etching adhesive on dentin for 15, 30 and 45 s exhibited similar thickness of the hybrid layer. As regards the resin tags, no statistically significant differences could be found between the study groups.Conclusions: it could be concluded that the increase in the time of application of the self-etching adhesive Adper Prompt L-Pop did not significantly influence the formation and thickness of hybrid layer, as well as its penetration into the sound dentin surface. (c) 2005 Elsevier Ltd. All rights reserved.

Evaluation of the Smear Layer and Hybrid Layer in Noncarious and Carious Dentin Prepared by Air Abrasion System and Diamond Tips

Purpose: To analyze the smear layer and the hybrid layer in noncarious and carious dentin prepared by different cutting instruments and restored with composite resin. Study design: Cavities were randomly prepared in 160 specimens (noncarious and artificial carious dentin) by high-speed diamond tips (KG Sorensen 1013), air abrasion system (Prepstart, Danville Engineering), ultrasonic tip (CVDentus 8.3231-1), and ultrasonic tip associated with ultrasonic cavitation by water for 10 s. Half of the cavities in each group were conditioned with 37% phosphoric acid for 15 s. The amount of smear layer and dentinal tubules present were analyzed using scanning electron microscopy and graded from 0 to 3. Cavities were prepared in another 20 noncarious specimens and 20 carious specimens and restored with adhesive composite resin system. The restorations were hemisected longitudinally and analyzed using scanning electron microscopy to evaluate the hybrid layer and resinous prolongation characteristics, using scores ranging from 1 to 6. Results: The data were statistically analyzed using Kruskal-Wallis and Dunn tests at 5% of significance level. There was evidence that the most efficient smear layer removal was the acid etching in the noncarious dentin and the water ultrasonic cavitation in the carious dentin. The hybrid layer formed on the noncarious and carious dentin prepared by the ultrasonic tip was more regular than in the specimens prepared by high-speed diamond tip, with many resinous prolongations. Conclusion: The ultrasonic tip seems to be a promising tool for carious dentin cavity preparation. Microsc. Res. Tech. 73:597-605, 2010. (C) 2009 Wiley-Liss, Inc.

In vivo preservation of the hybrid layer by chlorhexidine

Host-derived proteases have been reported to degrade the collagen matrix of incompletely-resin-infiltrated dentin. This study tested the hypothesis that interfacial degradation of resin-dentin bonds may be prevented or delayed by the application of chlorhexidine (CHX), a matrix metalloproteinase inhibitor, to dentin after phosphoric acid-etching. Contralateral pairs of resin-bonded Class I restorations in non-carious third molars were kept under intra-oral function for 14 months. Preservation of resin-dentin bonds was assessed by microtensile bond strength tests and TEM examination. In vivo bond strength remained stable in the CHX-treated specimens, while bond strength decreased significantly in control teeth. Resin-infiltrated dentin in CHX-treated specimens exhibited normal structural integrity of the collagen network. Conversely, progressive disintegration of the fibrillar network was identified in control specimens. Auto-degradation of collagen matrices can occur in resin-infiltrated dentin, but may be prevented by the application of a synthetic protease inhibitor, such as chlorhexidine.

Influence of voids in the hybrid layer based on self-etching adhesive systems: a 3-D FE analysis

The presence of porosities at the dentin/adhesive interface has been observed with the use of new generation dentin bonding systems. These porosities tend to contradict the concept that etching and hybridization processes occur equally and simultaneously. Therefore, the aim of this study was to evaluate the micromechanical behavior of the hybrid layer (HL) with voids based on a self-etching adhesive system using 3-D finite element (FE) analysis. Three FE models (Mr) were built: Mr, dentin specimen (41x41x82 μm) with a regular and perfect (i.e. pore-free) HL based on a self-etching adhesive system, restored with composite resin; Mp, similar to M, but containing 25% (v/v) voids in the HL; Mpp, similar to Mr, but containing 50% (v/v) voids in the HL. A tensile load (0.03N) was applied on top of the composite resin. The stress field was obtained by using Ansys Workbench 10.0. The nodes of the base of the specimen were constrained in the x, y and z axes. The maximum principal stress (σmax) was obtained for all structures at the dentin/adhesive interface. The Mpp showed the highest peak of σmax in the HL (32.2 MPa), followed by Mp (30 MPa) and Mr (28.4 MPa). The stress concentration in the peritubular dentin was high in all models (120 MPa). All other structures positioned far from voids showed similar increase of stress. Voids incorporated into the HL raised the σmax in this region by 13.5%. This behavior might be responsible for lower bond strengths of self-etching and single-bottle adhesives, as reported in the literature.

Correlation of the hybrid layer thickness and resin tags length with the bond strength of a self-etching adhesive system.

The objective of this study was to measure the thickness of the hybrid layer (HLT), length of resin tags (RTL) and bond strength (BS) in the same teeth, using a self-etching adhesive system Adper Prompt L Pop to intact dentin and to analyze the correlation between HLTand RTL and their BS. Ten human molars were used for the restorative procedures and each restored tooth was sectioned in mesio-distal direction. One section was submitted to light microscopy analysis of HLT and RTL (400x). Another section was prepared and submitted to the microtensile bond test (0.5 mm/min). The fractured surfaces were analyzed using scanning electron microscopy to determine the failure pattern. Correlation between HLT and RTL with the BS data was analyzed by linear regression. The mean values of HLT, RTL and BS were 3.36 microm, 12.97 microm and 14.10 MPa, respectively. No significant relationship between BS and HLT (R2= 0.011, p>0.05) and between BS and RTL (R2= 0.038) was observed. The results suggested that there was no significant correlation between the HLT and RTL with the BS of the self-etching adhesive to dentin.

Observation of tags and hybrid layer of a single bottle conventional adhesive system and a self-etching adhesive system, on sound dentin.

This experimental light microscopy study investigated the formation of a hybrid layer and resin tags on sound dentin, after utilization of conventional and self-etching adhesive systems. After restorative procedures, the specimens were decalcified in a formic acid and sodium citrate solution, embedded in paraffin, sectioned at 6-microm thickness and stained by the Brown & Brenn method for analysis and measurement by light microscopy (AXIOPHOT) (400x). The results were statistically analyzed by analysis of variance, at a significance level of 5%. Based on the results, it could be concluded that the conventional adhesive allowed the formation of a thicker hybrid layer than the self-etching adhesive, with similar penetration into the dentinal tubules (resin tags).

Analysis of hybrid layer thickness, resin tag length and their correlation with microtensile bond strength using a total etch adhesive to intact dentin.

The objective of this study was to evaluate the use of a two-step total etch and rinse adhesive, the correlation between the hyybrid layer thickness (HL) and bond strength (BS), and between resin tag length (RT) and bond strength in the same teeth, and also to evaluate the fracture patterns of the tested specimens. Ten human molars were used for the restorative procedure and then sectioned in two halves (mesio-distally). The materials used were Adper Single Bond 2, 3M ESPE, Ultra etch gel, Ultradent and Filtek Z250, 3M ESPE. One half were utilized to measure the HL thickness and RT length through light microscopy analysis (400x), and the other half was subject to a microtensile test to measure the BS. The fractured surfaces were analyzed by scanning electron microscopy and fracture patterns classified. The Pearson correlation test was applied (p = 0.05). The results of the analyses of each specimen then were correlated: mean HL thickness = 4.39 (0.48) microm, mean length of RT = 9.94 (1.69) microm, mean BS = 23.98 (10.24) MPa. A statistically significant correlation between HL thickness and bond strength was found (r = 0.93). The two step etch and rinse adhesive system, showed a strong correlation between HL thickness and bond strength. The most common fractures were adhesive, followed by cohesive in resin.

Influence of the hybrid layer thickness and resin tag length on microtensile bond strength.

The purpose of this study was to evaluate the correlation between the hybrid layer thickness/resin tag length and the microtensile bond strength of conventional two-step adhesive system, when applied to healthy dentinal tissue. After performing the restorative adhesive procedures and tooth extractions, ten specimens were sectioned in the mesiodistal direction. One section was used for microscopic analysis of the resin tag lengths and the hybrid layer thickness, while the other was used for the microtensile bond strength test (0.5 mm/min). The fractured surface was classified according to the fracture pattern, under a stereoscopic microscope at 40x magnification. Data obtained were submitted to analysis using one-way ANOVA and Pearson's Correlation test (alpha=0.05). The means corresponding to the hybrid layer thickness, resin tag lengths and the microtensile test were 2.68 microm, 6.43 microm and 16.23 MPa, respectively. There was no correlation between the means of the values obtained for the microtensile test, and those presented by the hybrid layer (r2=0.40, p>0.05) and resin tags (r2=0.21, p>0.05). The microtensile bond strength of the conventional two-step adhesive system Adper Single Bond 2 did not depend on the thickness of the hybrid layer and length of resin tags.

Influence of cutting instruments and adhesive systems on hybrid layer formation.

Influence of cutting instruments and The aim of this study was to analyze the hybrid layer in noncarious dentin prepared by different cutting instruments and restored with composite resin. The cavities were randomly prepared in 40 specimens using a high-speed diamond bur (KG Sorensen 1013) and an ultrasonic tip (CVDentus C22). The cavities were restored with composite resin by varying the adhesive system between the Adper™ Single Bond (2 x 1 system, primer+adhesive) and the Prompt L-Pop™ (3 x 1 system, self-etching). The restorations were hemisected longitudinally and analyzed in the SEM (Scanning electron microscopy) in order to evaluate the hybrid layer and resinous tags characteristics, using scores ranging from 1 to 6. The Pearson test revealed a high correlation coefficient and good significance levels for both intra- and inter-raters values (r=0.90). The data were statistically analyzed using the Mann-Whitney test (P≤0.05). A larger proportion of regular hybrid layers with numerous tags were observed in the dentin prepared using the high-speed diamond burs and restored with a 2 × 1 adhesive system. Alternatively, the 3 × 1 adhesive system promoted the generation of a thin hybrid layer with few tags. After preparation using an ultrasonic tip revealed few or no tags after the preparation and 2 × 1 or 3 × 1 adhesive system application. The high-speed diamond burs produced a dentin surface that was more favorable to restorative material adhesion than the ultrasonic tips, regardless of the adhesive system used.

Correlation between hybrid layer thickness, resin tag length and microtensile bond strength of a self-etching adhesive system

The purpose of this study was to evaluate the correlation between the hybrid layer thickness, resin tag length and resin bond strength of a self-etching adhesive system to sound dentin tissue in vivo. After performing restorative procedures and tooth extractions, ten specimens were sectioned in a mesiodistal direction. One dental section was used for light microscope analysis, in which both the resin tag length and hybrid layer thickness were measured, while the other section was analyzed using a microtensile test (0.5 mm/min). The fractured surface of the latter section was characterized using a stereoscopic magnifying glass (40x magnifcation). The results were subject to statistical analysis using the Pearson Correlation Test (a = 0.05). The hybrid layer thickness, resin tag length and resin bond strength mean values were 2.19 microm (0.34), 4.34 microm (0.28) and 9.73 MPa (5,55), respectively. In addition, correlation tests between the resin tag length and the resin bond strength (r=0.014) and also between the hybrid layer thickness and bond strength (r=0.43), showed no statistically significant correlation. The microtensile bond strength of Adper Prompt L Pop self-etching adhesive system does not depend on hybrid layer thickness or resin tag length.