Effects on dentin nanomechanical properties, cell viability and dentin wettability of a novel plant-derived biomodification monomer.

OBJECTIVES: To evaluate the effects of dentin biomodification agents (Proanthocyanidin (PAC), Cardol (CD) and Cardol-methacrylate (CDMA) on dentin hydrophilicity by contact angle measurement, viability of dental pulp stem cells (DPSCs) and nanomechanical properties of the hybrid layer (HL). METHODS: CDMA monomer was synthesized from cardol through methacrylic acid esterification. Human extracted third molars were used for all experiments. For nanomechanical tests, specimens were divided in four groups according to the primer solutions (CD, CDMA, PAC and control) were applied before adhesive and composite coating. Nanomechanical properties of the HL were analyzed by nanoindentation test using a Berkovich probe in a nanoindenter. Wettability test was performed on dentin surfaces after 1 min biomodification and measured by contact angle analysis. Cytotoxicity was assessed by a MTT assay with DPSCs after 48 and 72 h. Data were analyzed with Student's t test or Two-way ANOVA and Tukey HSD test (p < 0.05). RESULTS: CD and CDMA solutions achieved greater hydrophobicity and increased the water-surface contact angles when compared to PAC and control groups (p < 0.05). PAC group showed a greater reduction of elastic modulus in nanoindentation experiments when compared to CD and CDMA groups (p < 0.05) after 4 months of aging. CD inhibited cell proliferation compared to all further materials (p < 0.05), whilst CDMA and PAC indicated no cell cytotoxicity to human DPSCs. SIGNIFICANCE: Cardol-methacrylate provided significantly higher hydrophobicity to dentin and demonstrated remarkable potential as collagen crosslinking, attaining the lowest decrease of HL's mechanical properties. Furthermore, such monomer did not affect pulp cytotoxicity, thereby highlighting promising feasibility for clinical applications.

Atmospheric water harvesting using functionalized carbon nanocones.

In this work, we propose a method to harvest liquid water from water vapor using carbon nanocones. The condensation occurs due to the presence of hydrophilic sites at the nanocone entrance. The functionalization, together with the high mobility of water inside nanostructures, leads to a fast water flow through the nanostructure. We show using molecular dynamics simulations that this device is able to collect water if the surface functionalization is properly selected.

Blue Titania: The Outcome of Defects, Crystalline-Disordered Core-Shell Structure, and Hydrophilicity Change.

In this research, changes in several characteristics of partially reduced titania were studied. The reduction process used made it possible to gradually observe changes in the material depending on the amount of reducing agent used. We used NaBH4 to impregnate commercial TiO2 with isopropyl alcohol. Impregnated TiO2 nanoparticles were dried and thermally treated in a nitrogen flow to obtain blue titania samples. Thorough spectroscopic characterization showed that oxygen atoms from hydroxyl groups, as well as from the surface, and the lattice of TiO2 was consumed. This caused changes in the surface and even in the bulk of TiO2 when the amount of reducing agent used was increased. Structural, optical, superficial, and textural characteristics were studied using XRD, Raman, DRS UV-Vis-NIR, Mid-DRIFT, XPS, and nitrogen adsorption/desorption isotherms. A photocatalytic test of the degradation of methylene blue dye was performed. Among different effects on the mentioned characteristics, we found evidence of changes in the surface properties of the blue titania samples and their probable effect on the photocatalytic properties. The reduction process implied a preponderant decrease in the surface hydrophilicity of the reduced samples, an effect shown for the first time in this type of material.

Switchable-hydrophilicity solvent-based liquid-phase microextraction in an on-line system: Cobalt determination in food and water samples.

An on-line system employing switchable-hydrophilicity solvent-based liquid-phase microextraction (SHS-LPME) is described in this work. The method is based on the preconcentration of the species formed between cobalt and the reagent 1-nitroso-2-naphthol (NN), with subsequent detection by digital image colorimetry. The system's operation begins with the on-line mixture of sample, switchable solvent, and an alkaline agent in a reaction coil. Then the mixture is transported to an extraction chamber. The introduction of a proton donor leads to the passage of the solvent to its hydrophobic form, which allows phase separation. The rich phase is then directed to a glass tube, where detection is performed. Octanoic acid, sodium carbonate, and sulfuric acid were used as the extraction solvent, the alkaline agent, and the proton donor, respectively. Under optimized conditions, the method presented a detection limit of 0.8 µg L-1 and an enrichment factor of 41. The precision obtained was 4.8% (20 µg L-1). The accuracy of the method was tested by the analysis of Tomato Leaves certified reference material (NIST 1573a). The method was applied to the determination of cobalt in food, dietary supplements, and water samples. The method is presented as a green alternative and very accessible to the determination of cobalt in the analyzed samples.

Influence of saliva interaction on surface properties manufactured for rapid osseointegration in dental implants.

Surface treatments are designed to promote modified implant surfaces with positive interactions with the surrounding living tissues. However, the inadvertent early contact of these surfaces with oral fluids during surgery may lead to undesired conditions affecting osseointegration. This study aimed to investigate the possible alterations in the physico-chemical properties of modified-surfaces caused by early saliva exposure. Titanium (Ti) surfaces were exposed to three different samples of human saliva and later analyzed for protein adhesion, physico-chemical surface alterations, and osteogenic cell-viability. The results indicated that surface roughness was the most significant factor influencing saliva protein adsorption; moreover, hydrophilic surfaces had critically lost their characteristics after contact with saliva. Decreased cell viability was observed in cultures after contact with saliva. Early contact with saliva might negatively influence modified surface properties and local cell viability. Careful surgical insertion of implants with hydrophilic surfaces is recommended, particularly in sites where saliva interaction is prone to occur.

Impact of MWCO and Dopamine/Polyethyleneimine Concentrations on Surface Properties and Filtration Performance of Modified Membranes.

The mussel-inspired method has been investigated to modify commercial ultrafiltration membranes to induce antifouling characteristics. Such features are essential to improve the feasibility of using membrane processes in protein recovery from waste streams, wastewater treatment, and reuse. However, some issues still need to be clarified, such as the influence of membrane pore size and the polymer concentration used in modifying the solution. The aim of the present work is to study a one-step deposition of dopamine (DA) and polyethyleneimine (PEI) on ultrafiltration membrane surfaces. The effects of different membrane molecular weight cut-offs (MWCO, 20, 30, and 50 kDa) and DA/PEI concentrations on membrane performance were assessed by surface characterization (FTIR, AFM, zeta potential, contact angle, protein adsorption) and permeation of protein solution. Results indicate that larger MWCO membranes (50 kDa) are most benefited by modification using DA and PEI. Moreover, PEI is primarily responsible for improving membrane performance in protein solution filtration. The membrane modified with 0.5:4.0 mg mL-1 (DA: PEI) presented a better performance in protein solution filtration, with only 15% of permeate flux drop after 2 h of filtration. The modified membrane can thus be potentially applied to the recovery of proteins from waste streams.

Extension of hydrophilicity stability by reactive plasma treatment and wet storage on TiO2 nanotube surfaces for biomedical implant applications.

Micro and nanoscale changes allow the optimization of physico-chemical properties of titanium implant surfaces. Recently UV and plasma treatments have allowed surface hydrophilicity to take increased prominence; however, this beneficial effect is short-lived. The aim of this study is to investigate methodologies post-anodizing treatment to generate and maintain high surface hydrophilicity along with high biocompatibility. Anodized surfaces were characterized regarding physical-chemical properties. Then, surface wettability with nanomorphology was evaluated at different times and with distinct post-treatments: as deposited, with a reactive plasma and UV-light post-treatment, stored in air or deionized (DI) water. Adhesion, alkaline phosphatase (ALP) activity and bone cell viability tests were executed after the incremental treatments. The anodizing process generated a surface with TiO2 nanotubes morphology and micro-roughness. Plasma-treated surfaces resulted in the most hydrophilic samples and this property was maintained for a longer period when those were stored in DI water (angle variation of 7° to 12° in 21 days). Furthermore, plasma post-treatment changed the titanium surface crystalline phase from amorphous to anatase. Anodized surfaces modified by reactive plasma and stored in DI water suggest better hydrophilicity stability, biocompatibility, ALP activity and achievement of crystalline phase alteration, indicating future potential use on biomedical implants.

A green and low-cost method employing switchable hydrophilicity solvent for the simultaneous determination of antidepressants in human urine by gas chromatography - mass spectrometry detection.

In this study, the use of switchable hydrophilicity solvent with a simple and low-cost lab-made device for the extraction procedure in homogeneous liquid-liquid microextraction is proposed for the first time in the determination of antidepressants in human urine. The antidepressants studied consisted of fluoxetine, amitriptyline, nortriptyline, imipramine, desipramine and sertraline. The optimization of the main parameters that can influence on the extraction efficiency was performed through multivariate approaches. The analytes were separated and identified by gas chromatography coupled to mass spectrometry (GC-MS). The optimal extraction conditions consisted of using N,N-dimethylcyclohexylamine (DMCHA) as the switchable hydrophilicity solvent (SHS), 500 µL of urine sample previously diluted with ultrapure water at 1:1 ratio (v/v), 200 µL of a mixture of SHS:HCl 6 mol L-1 (1:1 v/v), 600 µL of NaOH 10 mol L-1 and 3 min of extraction time. A volume of 40 µL of diphenylamine at concentration of 500 µg L-1 (20 ng) was used as internal standard. The method developed was in-house validated, providing coefficients of determination higher than 0.995 for all analytes, limits of detection (LOD) from 0.02 to 0.88 µg L-1, limits of quantification (LOQ) from 0.05 to 2.92 µg L-1, relative recoveries of 68 to 102%, intra-day precision from 0.5 to 15.9%, inter-day precision from 4.2 to 19.3%, selectivity and robustness. The method proposed was successfully applied in five human urine samples from a Toxicological Information Center located in Porto Alegre (Brazil). The results demonstrated that the µP-SHS-HLLME approach is highly cost-effective, rapid, simple and environmentally-friendly with satisfactory analytical performance.

Improvement of Cr-Co-Mo Membrane Surface Used as Barrier for Bone Regeneration through UV Photofunctionalization: An In Vitro Study.

Although there are several studies of the ultraviolet (UV) light-mediated photofunctionalization of titanium for use as implant material, the underlying mechanism is not fully understood. However, the results of in vitro and in vivo studies are very encouraging. The use of UV photofunctionalization as a surface treatment on other implant materials, as the Cr-Co-Mo alloy, has not been explored in depth. Using sandblasted Cr-Co-Mo discs, the surface photofunctionalization was studied for ultraviolet A (UVA, 365 nm) and ultraviolet C (UVC, 254 nm), and the surfaces were evaluated for their ability to sustain hydroxyapatite crystal growth through incubation in simulated body fluid for a seven-day period. The variation of the pre- and post-irradiation contact angle and surface composition was determined through the quantification of the weight percentage of Ca and P crystals by the EDAX ZAF method (EDS). Statistically significant differences (p < 0.05) were found for samples irradiated with UVA over 48 h, corresponding with hydrophilic surfaces, and the same result was found for samples exposed to 3 h of UVC. Superhydrophilic surfaces were found in samples irradiated for 12, 24 and 48 h with UVC. The decrease in the carbon content is related with the increase in the surface content of Ca and P, and vice versa over the Cr-Co-Mo surfaces.

Hydrophilic surface of Ti6Al4V-ELI alloy improves the early bone apposition of sheep tibia.

OBJECTIVE: The aim of this preclinical study was to compare histologically and histomorphometrically both sandblasted/acid-etched implant surfaces with or without maintained in an isotonic solution of 0.9% sodium chloride in early stages of osseointegration. MATERIAL AND METHODS: Both implant surfaces were composed of a titanium/aluminum/vanadium alloy (Ti6Al4V-ELI), but they had different surface chemistries: sandblasted/acid-etched titanium surface (FN) or sandblasted/acid-etched surface maintained in an isotonic solution of 0.9% sodium chloride (FA). The surface morphology, topography and chemistry were evaluated by scanning electron microscopy (SEM), confocal microscopy (CM) and X-ray photoelectron spectroscopy (XPS), respectively. Dynamic contact angle (DCA) was employed for wettability evaluation. One implant from each group was placed in the left tibia of twenty healthy, skeletally mature Santa Ines sheep (n = 5). Bone area (BA) and bone-to-implant contact (BIC) were performed on thin sections (30 µm) at 7, 14, 21 and 28 days after implant installation. RESULTS: Despite the roughness and morphology similarities between the groups, at the XPS evaluation, the FA group presented 2.3 times less carbon on the surface (FN: 27.3% and FA: 11.6%), sharply enhanced hydrophilicity and significantly enhanced BA and BIC at 14, 21 and 28 days of healing (P < 0.05) compared with the FN. CONCLUSION: The data suggest that the hydrophilic FA accelerates the BA apposition and BIC interface around the implants during early stages of bone formation, providing highest degree of osseointegration.

Cytotoxicity of adhesive systems of different hydrophilicities on cultured odontoblast-like cells.

This study evaluated the cytotoxicity of experimental adhesive systems (EASs) on odontoblast-like cells. Paper discs (n = 132) were impregnated with 10 µL of each EAS-R1, R2, R3, R4, and R5 (in an ascending order of hydrophilicity), followed by photoactivation. R1 and R2 are nonsolvated hydrophobic blends, R3 represents a simplified etch-and-rinse adhesive system, and R4 and R5 represent simplified self-etch adhesive systems. Discs were immersed in Dulbecco's modified Eagle's medium for 24 h to obtain eluates applied on MDPC-23 cell cultures. No material was applied on discs used as control (R0). Cell viability [3-(4,5-dimethythiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay], total protein (TP) production, alkaline phosphatase (ALP) activity, type of cell death, and degree of monomer conversion Fourier transform infrared (%DC-FTIR) were evaluated. Data were analyzed by Kruskal-Wallis and Mann-Whitney tests (α = 0.05). Considering R0 (control) as having 100% of cell viability, R1, R2, R3, R4, and R5 reduced the metabolic activity of cells by 36.4, 3.1, 0.2, 21.5, and 65.7%, respectively, but only R1 and R5 differed from R0. Comparing with R0, lower TP production was observed for R1, R4, and R5, while ALP activity decreased for R1 and R5. Necrotic cell death was predominant for all EASs, but only R1, R4, and R5 differed from R0. Only R5 presented a different apoptotic cell death ratio from R0. R1 presented the lowest %DC (ca. 37%), whereas R4 and R5 presented the highest (ca. 56%). In conclusion, R2 and R3 were not toxic to the MDPC-23 cells, suggesting that the degree of hydrophilicity or %DC of the EASs alone were not responsible for their cytopathic effects.

Permeability of Dental Adhesives - A SEM Assessment.

OBJECTIVES: To morphologically evaluate the permeability of different commercial dental adhesives using scanning electron microscopy. METHODS: SEVEN ADHESIVE SYSTEMS WERE EVALUATED: one three-step system (Scotchbond Multi-Purpose - MP); one two-step self-etching primer system (Clearfil SE Bond - SE); three two-step etch-and-rinse systems (Single Bond 2 - SB; Excite - EX; One-Step - OS); and two single-step self-etching adhesives (Adper Prompt - AP; One-Up Bond F - OU). The mixture of primer and bond agents of the Clearfil SE Bond system (SE-PB) was also tested. The adhesives were poured into a brass mold (5.8 mm x 0.8 mm) and light-cured for 80 s at 650 mW/cm2. After a 24 h desiccation process, the specimens were immersed in a 50% ammoniac silver nitrate solution for tracer permeation. Afterwards, they were sectioned in ultra-fine slices, carbon-coated, and analyzed under backscattered electrons in a scanning electron microscopy. RESULTS: MP and SE showed slight and superficial tracer permeation. In EX, SB, and OS, permeation extended beyond the inner superficies of the specimens. SE-PB did not mix well, and most of the tracer was precipitated into the primer agent. In AP and OU, "water-trees" were observed all over the specimens. CONCLUSIONS: Different materials showed distinct permeability in aqueous solution. The extent of tracer permeation varied according to the composition of each material and it was more evident in the more hydrophilic and solvated ones.

Effect of relative humidities on microstructural, barrier and mechanical properties of Yam starch-monoglyceride films

The effect of monoglyceride on microstructural, barrier and mechanical properties of casted yam starch films were investigated in different relative humidities (RH) and compared with glycerol-starch films. A single screw extruder was used to produce the starch - monoglyceride complex before film production and this process was effective to inhibit the phase separation in films. The addition of the hydrophobic compound reduced hydrophobicity, transparency and water vapor permeability of films. This later value for starch-glycerol film (1.7 x 10-10 g Pa-1 s-1 m-1) was higher than starch (1.2 x 10-10 g Pa-1 s-1 m-1) and monoglyceride-starch films (1.0 x 10-10 g Pa-1 s-1 m-1). Films containing glycerol had higher relative crystallinity (B and V H) with a slight increase at higher RH values, while for monoglyceride films, the crystallinity was constant. Monoglyceride-starch films presented poor mechanical properties when compared to glycerol- starch ones but they presented a stable behavior under different relative humidities.

Estudou-se o efeito da adição de monoglicerídeo nas propriedades microestruturais, mecânicas e de barreira de filmes de amido de inhame, em diferentes umidades relativas (UR), comparando-as com as de filmes de amido- glicerol. Uma extrusora mono-rosca foi usado para produzir o complexo amido-monoglicerídeo, antes de produzir o filme, e o processo foi efetivo para inibir a separação de fases que geralmente ocorre nesse tipo de filmes. A adição de monoglicerídeo, que é um composto hidrofóbico, reduziu a hidrofilicidade, a transparência e a permeabilidade ao vapor de água dos filmes. O valor desta, para os filmes de amido-glicerol (1,7 x 10-10 g Pa-1 s-1 m-1) foi maior que para os de amido (1,2 x 10-10 g Pa-1 s-1 m-1) e para os de amido-monoglicerídeo (1,0 x 10-10 g Pa-1 s-1 m-1). Os filmes com glicerol tiveram maior cristalinidade relativa (B e V H), com um ligeiro aumento em altas UR, enquanto que nos filmes com monoglicerídeo a cristalinidade foi constante. Os filmes de amido-monoglicerídeo apresentaram piores propriedades mecânicas que os filmes de amido-glicerol, mas foram mais estáveis sob diferentes umidades relativas.