Evaluation of the Thermal, Chemical, Mechanical, and Microbial Stability of New Nanohybrids Based on Carboxymethyl-Scleroglucan and Silica Nanoparticles for EOR Applications.

Scleroglucan (SG) is resistant to harsh reservoir conditions such as high temperature, high shear stresses, and the presence of chemical substances. However, it is susceptible to biological degradation because bacteria use SG as a source of energy and carbon. All degradation effects lead to viscosity loss of the SG solutions, affecting their performance as an enhanced oil recovery (EOR) polymer. Recent studies have shown that nanoparticles (NPs) can mitigate these degradative effects. For this reason, the EOR performance of two new nanohybrids (NH-A and NH-B) based on carboxymethyl-scleroglucan and amino-functionalized silica nanoparticles was studied. The susceptibility of these products to chemical, mechanical, and thermal degradation was evaluated following standard procedures (API RP 63), and the microbial degradation was assessed under reservoir-relevant conditions (1311 ppm and 100 °C) using a bottle test system. The results showed that the chemical reactions for the nanohybrids obtained modified the SG triple helix configuration, impacting its viscosifying power. However, the nanohybrid solutions retained their viscosity during thermal, mechanical, and chemical degradation experiments due to the formation of a tridimensional network between the nanoparticles (NPs) and the SG. Also, NH-A and NH-B solutions exhibited bacterial control because of steric hindrances caused by nanoparticle modifications to SG. This prevents extracellular glucanases from recognizing the site of catalysis, limiting free glucose availability and generating cell death due to substrate depletion. This study provides insights into the performance of these nanohybrids and promotes their application in reservoirs with harsh conditions.

Synthesis and Characterization of New Nanohybrids Based on Carboxymethyl Scleroglucan and Silica Nanoparticles.

In this study, two new nanohybrids (NH-A and NH-B) were synthesized through carbodiimide-assisted coupling. The reaction was performed between carboxymethyl-scleroglucans (CMS-A and CMS-B) with different degrees of substitution and commercial amino-functionalized silica nanoparticles using 4-(dimethylamino)-pyridine (DMAP) and N,N'-dicyclohexylcarbodiimide (DCC) as catalysts. The morphology and properties of the nanohybrids were investigated by using transmission (TEM) and scanning electron microscopy (SEM), electron-dispersive scanning (EDS), attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FT-IR), X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-OES), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic light scattering (DLS). The nanohybrids exhibited differences in structure due to the incorporation of polyhedral oligomeric silsesquioxane (POSS) materials. The results reveal that hybrid nanomaterials exhibit similar thermal properties but differ in morphology, chemical structure, and crystallinity properties. Finally, a viscosity study was performed on the newly obtained nanohybrid materials; viscosities of nanohybrids increased significantly in comparison to the carboxymethyl-scleroglucans, with a viscosity difference of 7.2% for NH-A and up to 32.6% for NH-B.

Improving Riparin-A Dissolution through a Laponite Based Nanohybrid.

(1) Background: Riparin-A presents several pharmacological activities already elucidated, such as antimicrobial modulator, antileishmania, anxiolytic, anti-inflammatory, antinociceptive, and antioxidant. Even with important bioactive effects, the applicability of Riparin-A is limited due to its low solubility in water, impairing its dissolution in biological fluids. Thus, the objective of this study was to develop a nanohybrid based on Riparin-A and Laponite to obtain a better dissolution profile and evaluate its cytotoxic potential. (2) Methods: The formation of a hybrid system was highlighted by X-ray powder diffraction, infrared spectroscopy, and thermal analysis. Solubility, dissolution, and cytotoxicity studies were performed; (3) Results: An increase in the solubility and aqueous dissolution rate of Riparin-A was observed in the presence of clay. Diffractometric analysis of the hybrid system suggests the amorphization of Riparin-A, and thermal analyses indicated attenuation of decomposition and melting of the Riparin-A after interaction with clay. Furthermore, the nanosystem did not exhibit cytotoxic activity on normal and tumorigenic lines. (4) Conclusions: These results are promising for the development of the Riparin-A/Laponite nanosystem for therapeutic purposes, suggesting an increase in the range of possible routes of administration and bioavailability of this bioactive compound.

In Vitro Color Stability Evaluation of Three Polished and Unpolished Nanohybrid Resin Composites Immersed in a 0.12% Chlorhexidine-Based Mouthwash at Different Times.

The use of chlorhexidine-based mouthwashes on resin composites with rough surfaces can cause discoloration which compromises the esthetic of patients. The present study aimed to evaluate the in vitro color stability of Forma (Ultradent Products, Inc., South Jordan), Tetric N-Ceram (Ivoclar Vivadent, Schaan, Liechtenstein) and Filtek Z350XT (3M, ESPE, St. Paul, MN, USA) resin composites, with and without polishing, after being immersed in a 0.12% chlorhexidine (CHX)-based mouthwash at different times. The present in vitro experimental and longitudinal study used 96 nanohybrid resin composite blocks (Forma, Tetric N-Ceram and Filtek Z350XT) 8 mm in diameter and 2 mm thick, evenly distributed. Each resin composite group was divided into two subgroups (n = 16) with and without polishing and then immersed in a 0.12% CHX-based mouthwash for 7, 14, 21 and 28 days. Color measurements were performed with a calibrated digital spectrophotometer. Nonparametric tests were used to compare independent (Mann-Whitney U and Kruskal-Wallis) and related (Friedman) measures. In addition, the Bonferroni post hoc correction was used considering a significance level of p < 0.05. All polished and unpolished resin composites presented color variation < 3.3 when immersed for up to 14 days in 0.12% CHX-based mouthwash. The polished resin composite with the lowest color variation (ΔE) values over time was Forma, and the one with the highest values was Tetric N-Ceram. When comparing the color variation (ΔE) over time, it was observed that the three resin composites, with and without polishing, presented a significant change (p < 0.001), although these changes in color variation (ΔE) were evident from 14 days between each color acquisition (p < 0.05). The unpolished Forma and Filtek Z350XT resin composites showed significantly more color variation than the same polished ones at all times when immersed in a 0.12% CHX-based mouthwash for 30 s daily. In addition, every 14 days, all three resin composites with and without polishing showed a significant color change, while, every 7 days, color stability was maintained. All the resin composites showed clinically acceptable color stability when exposed for up to 14 days to the above-mentioned mouthwash.

Montmorillonite-Rifampicin Nanohybrid for pH-Responsive Release of the Tuberculostatic.

The present work describes the development of a hybrid and pH-responsive system for rifampicin using the clay mineral 'montmorillonite' as a nanocarrier. The influence of operational variables on the drug incorporation process was evaluated using 24 factorial designs. Under optimized conditions, the experiment allowed an incorporated drug dose equivalent to 98.60 ± 1.21 mg/g. Hybrid systems were characterized by different characterization techniques (FTIR, XRD, TGA, DSC, and SEM) to elucidate the mechanism of interaction between the compounds used. Through in vitro release studies, it was possible to verify the efficacy of the pH-dependent system obtained, with approximately 70% of the drug released after sixteen hours in simulated intestinal fluid. The adjustment of the experimental release data to the theoretical model of Higuchi and Korsmeyer-Peppas indicated that the release of rifampicin occurs in a prolonged form from montmorillonite. Elucidation of the interactions between the drug and this raw clay reinforces its viability as a novel carrier to develop an anti-TB/clay hybrid system with good physical and chemical stability.

Two birds with one stone: integrating exfoliation and immunoaffinity properties in multi-walled carbon nanotubes by non-covalent functionalization with human immunoglobulin G.

An innovative strategy is proposed to simultaneously exfoliate multi-walled carbon nanotubes (MWCNTs) and generate MWCNTs with immunoaffinity properties. This strategy was based on the non-covalent functionalization of MWCNTs with human immunoglobulin G (IgG) by sonicating 2.5 mg mL-1 MWCNTs in 2.0 mg mL-1 IgG for 15 min with sonicator bath. Impedimetric experiments performed at glassy carbon electrodes (GCE) modified with the resulting MWCNT-IgG nanohybrid in the presence of anti-human immunoglobulin G antibody (Anti-IgG) demonstrated that the immunoglobulin retains their biorecognition properties even after the treatment during the MWCNT functionalization. We proposed, as proof-of-concept, two model electrochemical sensors, a voltammetric one for uric acid quantification by taking advantages of the exfoliated MWCNTs electroactivity (linear range, 5.0 × 10-7 M - 5.0 × 10-6 M; detection limit, 165 nM) and an impedimetric immunosensor for the detection of Anti-IgG through the use of the bioaffinity properties of the IgG present in the nanohybrid (linear range, 5-50 µg mL-1; detection limit, 2 µg mL-1).

Surface roughness and oxygen inhibited layer control in bulk-fill and conventional nanohybrid resin composites with and without polishing: in vitro study.

BACKGROUND: It has been demonstrated that dental restorations with rough surfaces can have several disadvantages such as pigment retention or plaque accumulation, which can facilitate caries formation, color variation, loss of brightness, degradation of restoration, among others. The present study aimed to assess surface roughness in bulk fill and conventional nanohybrid resins with and without polishing, controlling the oxygen inhibited layer. METHODS: This in vitro and longitudinal experimental study consisted of 120 resin blocks of 6 mm diameter and 4 mm depth, divided into two groups: Bulk Fill (Tetric® N-Ceram Bulk-fill, Opus Bulk Fill APS, Filtek™ Bulk Fill) and conventional nanohybrid (Tetric® N-Ceram, Opallis EA2, Filtek™ Z250 XT). Each resin group was divided into two equal parts, placing glycerin only on one of them, in order to control the oxygen inhibited layer. Subsequently, the surface roughness was measured before and after the polishing procedure with Sof-Lex discs. The data were analyzed with the T-test for related measures, and for comparison between groups before and after polishing, the non-parametric Kruskal Wallis test with the Bonferroni post hoc was used, considering a significance level of p < 0.05. RESULTS: Before polishing, the resin composites with the lowest surface roughness were Opus Bulk Fill APS (0.383 ± 0.186 µm) and Opallis EA2 (0.430 ± 0. 177 µm) with and without oxygen inhibited layer control, respectively; while after polishing, those with the lowest surface roughness were Opus Bulk Fill APS (0.213 ± 0.214 µm) and Tetric N-Ceram (0.097 ± 0.099 µm), with and without oxygen inhibited layer control, respectively. Furthermore, before and after polishing, all resins significantly decreased their surface roughness (p < 0.05) except Opus Bulk Fill APS resin with oxygen inhibited layer control (p = 0.125). However, when comparing this decrease among all groups, no significant differences were observed (p < 0.05). CONCLUSION: The Opus Bulk Fill APS resin with oxygen inhibited layer control presented lower surface roughness both before and after polishing, being these values similar at both times. However, after polishing the other bulk fill and conventional nanohybrid resins with and without oxygen inhibited layer control, the surface roughness decreased significantly in all groups, being this decrease similar in all of them.

Raman, TEM, EELS, and Magnetic Studies of a Magnetically Reduced Graphene Oxide Nanohybrid following Exposure to Daphnia magna Biomarkers.

A ternary nanocomposite made of nanomaghemite, nanoanatase, and graphene oxide has been successfully synthesized using an inorganic coprecipitation approach, and it has been systematically investigated by X-ray diffraction, transmission electron microscopy, and different spectrocopic techniques (electron energy loss, µ-Raman, and 57Fe Mössbauer) after interaction with an effluent containing Daphnia magna individuals. Specifically, the influence of the nanocomposite over the Daphnia magna carapace, administered in two doses (0.5 mg mL-1 and 1 mg mL-1), has been characterized using µ-Raman spectroscopy before and after laser burning protocols, producing information about the physicochemical interaction with the biomarker. The thermal stability of the nanocomposite was found to be equal to 500 °C, where the nanoanatase and the nanomaghemite phases have respectively conserved their structural identities. The magnetic properties of the nanomaghemite have also been kept unchanged even after the high-temperature experiments and exposure to Daphnia magna. In particular, the size, texture, and structural and morphological properties of the ternary nanocomposite have not shown any significant physicochemical modifications after magnetic decantation recuperation. A significant result is that the graphene oxide reduction was kept even after the ecotoxicological assays. These sets of observations are based on the fact that while the UV-Vis spectrum has confirmed the graphene oxide reduction with a localized peak at 260 nm, the 300-K and 15-K 57Fe Mössbauer spectra have only revealed the presence of stoichiometric maghemite, i.e., the two well-defined static magnetic sextets often found in the bulk ferrimagnetic counterpart phase. The Mössbauer results have also agreed with the trivalent-like valence state of Fe ions, as also suggested by electron energy loss spectroscopy data. Thus, the ternary nanocomposite does not substantially affect the Daphnia magna, and it can be easily recovered using an ordinary magnetic decantation protocol due to the ferrimagnetic-like character of the nanomaghemite phase. Consequently, it shows remarkable physicochemical properties for further reuse, such as cleaning by polluted effluents, at least where Daphnia magna species are present.

Effect of Polishing on the Surface Microhardness of Nanohybrid Composite Resins Subjected to 35% Hydrogen Peroxide: An In vitro Study.

AIM: The use of bleaching agents, despite being a conservative treatment, can cause a decrease in the surface microhardness of dental resins, affecting their aesthetics and performance. The aim of this study was to evaluate the in vitro effect of polishing on the surface microhardness of nanohybrid composite resins that were subjected to bleaching with 35% hydrogen peroxide. MATERIALS AND METHODS: This cross-sectional, in vitro experimental study consisted of 30 composite resin samples made according to ISO 4049-2019 and divided equally into two groups (A and B) which were subjected to 35% hydrogen peroxide bleaching. Group A was subjected to polishing procedure, whereas group B was the control group. The samples were stored in distilled water at 37°C for 24 h. The Vickers microhardness was determined with a load of 100 g-f for 10 s. The data were analyzed with Student's t-test for independent samples at a confidence level of 95%. RESULTS: The surface microhardness of the group that was subjected to polishing (A) obtained a mean of 78.07 ± 7.96 HV, whereas for the group that was not subjected to polishing (B) the mean was 65.67 ± 5.22 HV. The difference between groups (A and B) was statistically significant (P < 0.001). CONCLUSION: Nanohybrid composite resins previously subjected to 35% hydrogen peroxide gel significantly increased their surface microhardness when subjected to polishing when compared with unpolished nanohybrid composite resins.

Effects of Different Light-curing Modes on the Compressive Strengths of Nanohybrid Resin-based Composites: A Comparative In Vitro Study.

OBJECTIVE: To evaluate the effects of polymerization conducted by using LED lamps of different wavelengths (polywave and monowave) on the compressive strengths of nanohybrid composite resins Filtek™ Bulk Fill - 3M and 3M™ Filtek™ Z350 XT. MATERIALS AND METHODS: The study was prospective, experimental in vitro, and comparative. The sample consisted of nanohybrid composite resins. The sample size (n) was 100 specimens, divided into 10 groups. CRIS (Checklist for Reporting In-vitro Studies) Guidelines were used for writing this article. RESULTS: There were statistically significant differences between all groups with P < 0.001. Group 2 (nanohybrid composite resin blocks 3M™ Filtek™ Z350 XT with Monowave LED lamps) showed the highest compressive strength of 238.36±34.69N; CI (213.55-263.18) N. This was followed by Group 4 (nanohybrid composite resin blocks 3M™ Filtek™ Z350 XT with Poliwave LED lamps, High Power) and Group 6 (nanohybrid composite resin blocks 3M™ Filtek™ Z350 XT with Poliwave LED lamps, Soft Star), with compressive strengths of 222.33 ± 53.09N, and 209.21 ± 22.52N, respectively. CONCLUSIONS: Significant differences were found between the compressive strengths of 3M™ Filtek™ Z350 XT and Filtek™ Bulk Fill - 3M resins, and that of resins photopolymerized with monowave and polywave LED lamps and halogen light. Thus, the types of light and lamp directly influence the compressive strengths of the composite resins.

Heterogeneous electro-Fenton process for degradation of bisphenol A using a new graphene/cobalt ferrite hybrid catalyst.

A simple, efficient, environmentally friendly, and inexpensive synthesis route was developed to obtain a magnetic nano-hybrid (GH) based on graphene and cobalt ferrite. Water with a high content of natural organic matter (NOM) was used as solvent and a source of carbon. The presence of NOM in the composition of GH was confirmed by FTIR and Raman spectroscopy, which evidenced the formation of graphene, as also corroborated by XRD analyses. The diffractograms and TEM images showed the formation of a hybrid nanomaterial composed of graphene and cobalt ferrite, with crystallite and particle sizes of 0.83 and 4.0 nm, respectively. The heterogeneous electro-Fenton process (EF-GH) achieved 100% degradation of bisphenol A (BPA) in 50 min, with 80% mineralization in 7 h, at pH 7, using a current density of 33.3 mA cm-2. The high catalytic performance was achieved at neutral pH, enabling substantial reduction of the costs of treatment processes. This work contributes to understanding the role of NOM in the synthesis of a magnetic nano-hybrid based on graphene and cobalt ferrite, for use in heterogeneous catalysis. This nano-hybrid has excellent potential for application in the degradation of persistent organic pollutants found in aquatic environments.

Review of nano-technology applications in resin-based restorative materials.

OBJECTIVE: Nanotechnology has progressed significantly and particles as small as 3 nm are being employed in resin-based restorative materials to improve clinical performance. The goal of this review is to report the progress of nanotechnology in Restorative Dentistry by reviewing the advantages, limitations, and applications of resin-based restorative materials with nanoparticles. MATERIALS AND METHODS: A literature review was conducted using PubMed/Medline, Scopus and Embase databases. In vitro, in vivo and in situ research studies published in English between 1999 and 2020, and which focused on the analysis of resin-based restorative materials containing nanoparticles were included. RESULTS: A total of 140 studies were included in this review. Studies reported the effect of incorporating different types of nanoparticles on adhesive systems or resin composites. Mechanical, physical, and anti-bacterial properties were described. The clinical performance of resin-based restorative materials with nanoparticles was also reported. CONCLUSIONS: The high surface area of nanoparticles exponentially increases the bioactivity of materials using bioactive nanofillers. However, the tendency of nanoparticles to agglomerate, the chemical instability of the developed materials and the decline of rheological properties when high ratios of nanoparticles are employed are some of the obstacles to overcome in the near future. CLINICAL SIGNIFICANCE: In spite of the recent advancements of nanotechnology in resin-based restorative materials, some challenges need to be overcome before new nano-based restorative materials are considered permanent solutions to clinical problems.

Control of microbial biofilm formation as an approach for biomaterials synthesis.

The search for new biomaterials with superior mechanical properties is the focus in the area of materials science. A promising pathway is drawing inspiration from nature to design and develop materials with enhanced properties. In this work, a novel strategy to produce functionalized supramolecular bionanomaterials from the microbial biofilm is reported. Tuneable biofilms with specific characteristics were obtained by controlling the culture condition of the microorganism. When the exopolysaccharide (EPS) production was desired the tryptone was the best nutritional component for the EPS production into the biofilm. However, for the expression of a high amount of amyloid protein the combination of peptone and glucose was the best nutritional choice. Each biofilm obtained showed its owner rheology properties. These properties were altered by the addition of extracellular DNA, which increased the viscosity of the biofilm and induced a viscoelastic hydrogel behavior. Besides, as a proof of concept of bionanomaterial, a novel supramolecular polymeric hybrid EPS-Amyloid protein (EPAP) was obtained from the biofilm and it was tested as a new natural functionalized support for enzyme immobilization. The results suggest that this technology could be used as a new concept to obtain biomaterials from biofilms by controlling the nutritional conditions of a microorganism. Understanding environmental factors affecting biofilm formation will help the development of methods for controlling biofilm production and therefore obtaining new biomaterials.

Luminescent Mesoporous Silica Nanohybrid Based on Drug Derivative Terbium Complex.

Mesoporous silica nanoparticles prepared by organic template-driven synthesis have been successfully explored as carriers of the drug-derivate green luminescent complex of terbium (III) with the nonsteroidal anti-inflammatory drug ketoprofen. The terbium (III) complex was synthesized by reacting ketoprofen sodium salt with terbium (III) chloride, which was further adsorbed onto the surface of mesoporous nanoparticles with a mean particle size of 47 ± 4 nm and pore size of 11 nm. The incorporation of the complex into mesoporous silica nanoparticles was tracked by the decrease in the surface area and pore size of the nanoparticles, and successfully demonstrated by substantial changes in the adsorption isotherms and thermal and vibrational spectroscopy results. The cytotoxicity assay and confocal microscopy have shown that the novel luminescent nanohybrid presents high cell viability and the characteristic terbium (III) emission can be assessed through two-photon excitation, which paves the way for bioimaging applications in nanomedicine.

Combination of Aryl Diselenides/Hydrogen Peroxide and Carbon-Nanotube/Rhodium Nanohybrids for Naphthol Oxidation: An Efficient Route towards Trypanocidal Quinones.

This work reports a combination of aryl diselenides/hydrogen peroxide and carbon-nanotube (CNT)/rhodium nanohybrids (RhCNT) for naphthol oxidation towards the synthesis of 1,4-naphthoquinones and evaluation of their relevant trypanocidal activity. Under a combination of (PhSe)2 /H2 O2 in the presence of O2 in iPrOH/hexane, several benzenoid (A-ring)-substituted quinones were prepared in moderate to high yields. We also studied the contribution of RhCNT as co-catalyst in this process and, in some cases, yields were improved. This method provides an efficient and versatile alternative for preparing A-ring-modified naphthoquinonoid compounds with relevant biological profile.

Electrochemical immunosensor based on ZnO nanorods-Au nanoparticles nanohybrids for ovarian cancer antigen CA-125 detection.

In this research, ZnO nanorods - Au nanoparticles nanohybrids have been fabricated and employed to sensitive electrochemical strategy for the specific detection of the ovarian cancer antigen CA-125/MUC126. The microdevice was developed in our lab based on gold and silver electrodes sputtered on glass substrate. The ZnO nanorods arrays were grown on working electrode using assisted microwave hydrothermal synthesis than gold nanoparticles (Au NPs) were deposited by sputtering. The Au NPs onto ZnO nanorods surface provides a favorable platform for efficient loading of anti-CA-125 antibody via binding with cystamine and glutaraldehyde. The effective loading of the biological material (CA-125 antibody and antigen) on the matrix was observed by SEM images. The electrochemical immunosensor shows a sensitive response to ovarian cancer antigen recombinant human CA-125/MUC126 with detection of 2.5ng/µL, 100 times lower than immunoblot system. Due to high specificity, reproducibility and noteworthy stability, the developed sensor will provide a sensitive, selective and convenient approach to be used to detect CA-125/MUC126.