Hybrid ceramic repair strength, surface roughness, and bond failure, using methylene blue-activated low-level laser therapy, Carbon dioxide, and Ti: Al2O3 laser.

AIMS: To evaluate the impact of various pretreatment regimes (LLLT, Ti-sapphire laser, CO2, and HFA-S) on hybrid ceramics, specifically focusing on their ability to enhance repair strength and minimize surface roughness (Ra). MATERIAL AND METHODS: Discs were made from hybrid ceramics and after disinfection were randomly divided into four groups based on different surface conditioning techniques. Each group consisted of 15 discs, resulting in a total sample size of 60. dics in group 1 was surface treated with Low-level laser therapy (LLLT) using methylene blue (MB), Discs in group 2 with Ti-sapphire laser, Discs in group 3 with CO2 laser, and discs in group 4 with HFA-S. Five samples from each group were assessed for Ra. The remaining 10 samples from each group underwent repair using a porcelain repair kit in adherence to the planned instructions. The bond strength of each sample in all groups was measured using a universal testing machine. Following the bond strength testing, the specimens from all study groups were analyzed to determine the mode of failure. To evaluate the data, a two-way analysis of variance (ANOVA) was used, followed by post hoc multiple comparisons. RESULTS: The highest repair bond strength was observed in group 4 hybrid ceramics pretreated with HFA-S (19.05±0.79 MPa). The lowest repair bond scores were observed in group 1 hybrid ceramics preconditioned with LLLT in the presence of Photosensitizer (13.41±0.36 MPa). The highest Ra scores were exhibited in group 2 surface treated with Ti-sapphire laser (0.0515±0.16 µm) and the lowest Ra scores were observed in Group 4 HFA-S (0.0311±0.79 µm). Predominant bond failure among different investigated groups was cohesive. CONCLUSION: The current gold standard for hybrid ceramic conditioning is the use of hydrofluoric acid (HFA) combined with a silane coupling agent. Low-level laser therapy with methylene blue photosensitizer is not recommended for the treatment of hybrid ceramics.

Kigelia africana fruit biofibre polysaccharide extraction and biofibre development by silane chemical treatment.

Silane-treated natural cellulosic Kigelia africana fruit fibre (KAF) was experimentally established to have strong strength after removing hydrophilic materials. Silane treatment makes it compatible with hydrophobic biopolymeric materials than existing non-grafted KA fibre. In this work, the polysaccharide was extracted from the KAF and found to have all the essential compounds. KA fruit-based cellulosic fibre was extracted and treated with different concentrations of silane solution. Silane-treated (13%) KAF has a cellulose content of about 76.86%. The peak found at 1734 cm-1 shows the hemicellulose in untreated fibres, and its intensity decreased after silane treatment, as confirmed by FTIR. X-ray diffraction investigation indicated that silane-treated (5%) KAF has a crystallinity index of 70.22%. After treatment, the tensile strength of 5% silane-treated KAF shows a tensile strength of 490.77 MPa, giving more viability to biofibre reinforcement.

MDP Salts: A New Bonding Strategy for Zirconia.

Durable resin-ceramic adhesion may influence the clinical success of ceramic restorations, which has been one of the challenging issues in dentistry. The present study assessed the bond strength and chemical interaction of 10-methacryloxydecyl dihydrogen phosphate (MDP), MDP+silane, and MDP-salt primers to alumina-blasted zirconia ceramic by tensile bond strength test, surface elemental composition with x-ray photoelectron spectroscopy analysis, contact angle measurement, surface morphology with scanning electron microscopy, and surface topography with 3-dimensional confocal laser scanning microscope analyses. MDP-salt showed the highest tensile bond strength before and after thermocycling when compared with MDP and MDP+silane (P < 0.05). The measured contact angle values differed significantly (P < 0.001) in the order of MDP-salt > control (no chemical pretreatment) > MDP+silane > MDP. There was no difference in surface roughness (P = 0.317) and surface topography among all tested groups. Zirconia treated with MDP-salt showed phosphorus peaks in addition to zirconia and alumina peaks. MDP-salt has zirconia priming properties, which improves bonding performance to resin cement.

Anchor and bridge functions of APTES layer on interface between hydrophilic starch films and hydrophobic soyabean oil coating.

One of the well-recognized weaknesses of starch-based materials is their sensitivity to moisture, which limits their expanding applications. Natural materials, soyabean oils have been used as a coating for starch film, but the poor interface between hydrophilic starch and hydrophobic soyabean oil needs to be improved. In this work, (3-Aminopropyl) triethoxysilane (APTES) was used to reinforce the bonding between starch matrix and the coating of bio-based acrylated epoxidized soyabean oil (AESO). Study results show that APTES interacted effectively with both starch films via hydrogen bonding, and chemical bonds with AESO through the Michael addition reaction. Pull adhesion and cross-cutting tests demonstrated that the interfacial adhesion was significantly improved after treating their surface with APTES. The interfacial adhesion strength increased over 4 times after treating with 1.6 wt% APTES. The starch films treated with APTES and AESO coating were intact after soaking in water for more than 2 h.

Fabrication of a Kagomé-type MOF Membrane by Seeded Growth on Amino-functionalized Porous Al2 O3 Substrate.

In this study, we report an efficient fabrication method for the membrane of a metal-organic framework (MOF) (Kgm-OEt) which is one kind of kagomé-type MOF with a two-dimensional (2D) sheet structure having one-dimensional (1D) channels suitable for separation of H2 from other larger gases. The Kgm-OEt seed layer was created on an Al2 O3 substrate using layer-by-layer (LBL) growth, then a membrane was fabricated by secondary growth. The membrane on a 3-aminopropyltriethoxysilane (APTEs)-treated substrate obtained in this method was continuous and defect-free with the crystal orientation suitable for gas transportation, while the membrane grown on an unmodified substrate was loosely packed with unfavorable crystal orientation.

Biobased Polyurethane Composite Foams Reinforced with Plum Stones and Silanized Plum Stones.

In the following study, ground plum stones and silanized ground plum stones were used as natural fillers for novel polyurethane (PUR) composite foams. The impact of 1, 2, and 5 wt.% of fillers on the cellular structure, foaming parameters, and mechanical, thermomechanical, and thermal properties of produced foams were assessed. The results showed that the silanization process leads to acquiring fillers with a smoother surface compared to unmodified filler. The results also showed that the morphology of the obtained materials is affected by the type and content of filler. Moreover, the modified PUR foams showed improved properties. For example, compared with the reference foam (PUR_REF), the foam with the addition of 1 wt.% of unmodified plum filler showed better mechanical properties, such as higher compressive strength (~8% improvement) and better flexural strength (~6% improvement). The addition of silanized plum filler improved the thermal stability and hydrophobic character of PUR foams. This work shows the relationship between the mechanical, thermal, and application properties of the obtained PUR composites depending on the modification of the filler used during synthesis.

A signal-on electrochemical aptasensor based on silanized cellulose nanofibers for rapid point-of-use detection of ochratoxin A.

An innovative ultrasensitive electrochemical aptamer-based sensor was developed for ochratoxin A (OTA) detection in cold brew coffee through revolutionary combination of nanofibers, electrochemical method, and aptamer technologies. The assembly of the aptasensor was based on the activation of silanized cellulose nanofibrous membranes as a supporting matrix for methylene blue (MB) redox probe-labeled aptamer tethering. Cellulose nanofibrous membranes were regenerated by deacetylating electrospun cellulose acetate nanofibrous membranes with deacetylation efficacy of 97%, followed by silanization of the nanofiber surfaces by using (3-aminopropyl)triethoxysilane (APTES). A replacement of conventionally casted membranes by the nanofibrous membranes increased the active surface area on the working electrode of a screen-printed three-electrode sensor by more than two times, consequently enhancing the fabricated aptasensor performance. The developed aptasensor demonstrated high sensitivity and specificity toward OTA in a range 0.002-2 ng mL-1, with a detection limit of 0.81 pg mL-1. Moreover, the assembled aptamer-based sensor successfully detected OTA in cold brew coffee samples without any pretreatment. The aptasensor exhibited good reusability and stability over long storage time. Graphical abstract.

Biodegradable functional chitosan membrane for enhancement of artemisinin purification.

Artemisinin is mainly derived from Artemisia annua L. Since the leaves composition is complex, artemisinin purification faces great challenges. In this work, functional chitosan membranes were fabricated by a one-step hydrolysis method through grafting long-chain alkyl group on the surface of chitosan to increase its hydrophobicity. The as-prepared membranes were used to adsorb wax oil (i.e., the impurity components) in Artemisia annua L. and to avoid co-precipitation of wax oil along with artemisinin using the crystallization technique for purification. Octyl-trimethoxysilane modified chitosan membrane (FCM-C8) showed excellent capability to intensify this purification process. The product purity could reach more than 98 % using one crystallization step under the optimal conditions, and in this case, adsorption capacity of FCM-C8 for wax oil was 478.9 mg/g. In addition, the adsorption kinetics and mechanism of wax oil on FCM-C8 were studied. The membrane can simultaneously adsorb multiple components in wax oil through interactions like electrostatic forces, hydrogen bondings.

Effects of silylated starch structure on hydrophobization and mechanical properties of thermoplastic starch foams made from potato starch.

Non-biodegradable single use packaging are a serious environmental problem as it generates large amounts of waste and is generally not recycled. These packages, especially those made of expanded polystyrene, can be replaced by thermoplastic starch foams. These foams have the advantage of being from renewable sources and biodegradable. However, this material is hydrophilic and becomes unusable when it is exposed to water. Hydrophobizing starch comes as an alternative to make the foams more resistant to contact with water. The purpose of the modification is to exchange starch hydroxyl groups for less polar groups such as silane groups. In this work, two silanes were used for starch silylation: 3-chloropropyl trimethoxysilane and Methyltrimethoxysilane. The foams were made using four materials: modified starch, gelatinized starch, polyvinyl alcohol and water. Results from water absorption tests and mechanical tests show that foams absorb less water and become more resistant with the addition of silylated starch.

A pH-responsive dissociable mesoporous silica-based nanoplatform enabling efficient dual-drug co-delivery and rapid clearance for cancer therapy.

The balance between tumor accumulation and renal clearance has severely limited the efficacy of mesoporous silica-based drug nanocarriers in cancer therapy. Herein, a pH-responsive dissociable mesoporous silica-based nanoplatform with efficient dual-drug co-delivery, tumor accumulation and rapid clearance for cancer therapy is achieved by adjusting the wetting of the mesoporous silica surface. At pH 7.4, the synthesized spiropyran- and fluorinated silane-modified ultrasmall mesoporous silica nanoparticles (SP-FS-USMSN) self-assemble to form larger nanoclusters (denoted as SP-FS-USMSN cluster) via hydrophobic interactions, which can effectively co-deliver anticancer drugs, doxorubicin hydrochloride (Dox) and curcumin (Cur), based on the mesopores within SP-FS-USMSN and the voids among the stacked SP-FS-USMSN. At pH 4.5-5.5, the conformational conversion of spiropyran from a "closed" state to an "open" state causes the wetting of the SP-FS-USMSN surface, leading to the dissociation of the SP-FS-USMSN cluster for drug release and renal clearance. The in vitro and in vivo studies demonstrate that the Cur and Dox co-loaded SP-FS-USMSN cluster (Cur-Dox/SP-FS-USMSN cluster) possesses great combined cytotoxicity, and can accumulate into tumor tissue by its large size-favored EPR effect and potently suppress tumor growth in HepG2-xenografted mice. This research demonstrates that the SP-FS-USMSN cluster may be a promising drug delivery system for cancer therapy and lays the foundation for practical mesoporous silica-based nanomedicine designs in the future.

A novel and simple oral colon-specific drug delivery system based on the pectin/modified nano-carbon sphere nanocomposite gel films.

The 3-aminopropyltriethoxysilane modified nano-carbon sphere (MNCS) was added into pectin-Ca2+ film to improve the controlled release properties of the pectin-based oral colon-specific drug delivery system (OCDDS). The FT-IR measurements indicated the successful modification of nano-carbon sphere via silylation reaction and the electrostatic interaction between the pectin molecules and MNCS in the composite film. The FE-SEM showed the pore structure when the MNCS was mingled with the pectin. The 5-fluorouracil (5-FU) was employed as the drug model and the controlled release properties of the corresponding OCDDSs were determined. The values of the encapsulation efficiency ranged from 30.1% to 52.6%. All composite film based OCDDSs presented higher encapsulation efficiency than single pectin-Ca2+ based OCDDS. The drug release studies emerged that almost all the OCDDSs from composite films presented better release properties than single pectin-Ca2+ based OCDDS. The sample C revealed best release performance with the cumulative release rate of 32.17%, 22.77% and 63.89% in the simulated gastric fluid, small intestinal fluid and colon fluid, respectively. In addition, the kinetics studies were performed to analyze the release data. The cytotoxicity assay indicated good biocompatibility of the composite carriers.

Antimicrobial and Physicochemical Properties of Artificial Saliva Formulations Supplemented with Core-Shell Magnetic Nanoparticles.

Saliva plays a crucial role in oral cavity. In addition to its buffering and moisturizing properties, saliva fulfills many biofunctional requirements, including antibacterial activity that is essential to assure proper oral microbiota growth. Due to numerous extra- and intra-systemic factors, there are many disorders of its secretion, leading to oral dryness. Saliva substitutes used in such situations must meet many demands. This study was design to evaluate the effect of core-shell magnetic nanoparticles (MNPs) adding (gold-coated and aminosilane-coated nanoparticles NPs) on antimicrobial (microorganism adhesion, biofilm formation), rheological (viscosity, viscoelasticity) and physicochemical (pH, surface tension, conductivity) properties of three commercially available saliva formulations. Upon the addition of NPs (20 µg/mL), antibacterial activity of artificial saliva was found to increase against tested microorganisms by 20% to 50%. NPs, especially gold-coated ones, decrease the adhesion of Gram-positive and fungal cells by 65% and Gram-negative bacteria cells by 45%. Moreover, the addition of NPs strengthened the antimicrobial properties of tested artificial saliva, without influencing their rheological and physicochemical properties, which stay within the range characterizing the natural saliva collected from healthy subjects.

Magnetic C60 nanospheres based solid-phase extraction coupled with isotope dilution gas chromatography-mass spectrometry method for the determination of sixteen polycyclic aromatic hydrocarbons in Chinese herbal medicines.

C60-based magnetic nanospheres were synthesized by coating Fe3O4 nanospheres with silica, then modifying with 3-aminopropyltriethoxysilane as a linker and a C60 fullerene stationary phase. The morphologies, magnetic properties, infrared absorption and carbon content of magnetic nanospheres were studied by TEM, VSM, FTIR and carbon and sulfur analyzer. The magnetic nanospheres were employed for the magnetic solid-phase extraction (MSPE) of 16 polycyclic aromatic hydrocarbons (PAHs) in nine Chinese herbal medicines. The analyses were conducted by isotope dilution gas chromatography-mass spectrometry. The main parameters influencing the extraction, including extraction solvent, adsorbent amount, and extraction time were optimized. Method validation showed that the limit of detection (LOD) was 0.02-0.11 µg/kg, and the limit of quantification (LOQ) was 0.07-0.36 µg/kg. The spiked recoveries rates for 16 PAHs in white peony root were 84.7-107.2%. The relative standard deviation (RSD) was 1.7-8.4%. The established method was further used for the determination 16 PAHs in nine Chinese herbal medicines. Total content of 16 PAHs varied from 73.6 µg/kg (fructus lycii) to 2172.6 µg/kg (astragalus root). The results indicate that the pollution of PAHs in Chinese herbal medicines is serious. The established method can effective detect PAHs contamination in Chinese herbal medicines.

Therapeutic Efficiency of Multiple Applications of Magnetic Hyperthermia Technique in Glioblastoma Using Aminosilane Coated Iron Oxide Nanoparticles: In Vitro and In Vivo Study.

Magnetic hyperthermia (MHT) has been shown as a promising alternative therapy for glioblastoma (GBM) treatment. This study consists of three parts: The first part evaluates the heating potential of aminosilane-coated superparamagnetic iron oxide nanoparticles (SPIONa). The second and third parts comprise the evaluation of MHT multiple applications in GBM model, either in vitro or in vivo. The obtained heating curves of SPIONa (100 nm, +20 mV) and their specific absorption rates (SAR) stablished the best therapeutic conditions for frequencies (309 kHz and 557 kHz) and magnetic field (300 Gauss), which were stablished based on three in vitro MHT application in C6 GBM cell line. The bioluminescence (BLI) signal decayed in all applications and parameters tested and 309 kHz with 300 Gauss have shown to provide the best therapeutic effect. These parameters were also established for three MHT applications in vivo, in which the decay of BLI signal correlates with reduced tumor and also with decreased tumor glucose uptake assessed by positron emission tomography (PET) images. The behavior assessment showed a slight improvement after each MHT therapy, but after three applications the motor function displayed a relevant and progressive improvement until the latest evaluation. Thus, MHT multiple applications allowed an almost total regression of the GBM tumor in vivo. However, futher evaluations after the therapy acute phase are necessary to follow the evolution or tumor total regression. BLI, positron emission tomography (PET), and spontaneous locomotion evaluation techniques were effective in longitudinally monitoring the therapeutic effects of the MHT technique.

Cellulose nanofibers coated with silver nanoparticles as a flexible nanocomposite for measurement of flusilazole residues in Oolong tea by surface-enhanced Raman spectroscopy.

Cellulose nanofibers (CNF) coated with inorganic nanoparticles are novel hybrid nanocomposites that have great potential in various areas including agriculture and food science. The objectives of this study were to synthesize nanocomposites consisted of CNF coated with silver nanoparticles (AgNPs), which can be used as a surface-enhanced Raman spectroscopy (SERS) platform for measuring pesticides in Oolong tea. CNF were coated with AgNPs to form uniform CNF-AgNP nanocomposites that were investigated by transmission electron microscopy. Three-dimensional and porous CNF structures were loaded with AgNPs with an average size of 41 nm. CNF-AgNP substrates were applied in characterization and measurement of flusilazole in Oolong tea samples by SERS. A detection limit of 0.5 mg/kg for flusilazole was obtained based on partial least squares (PLS) regression analysis. These results indicate that CNF-AgNP nanocomposites combined with SERS is an accurate, sensitive, and efficient technique for identification and quantification of pesticide residues in Oolong tea.

Pectin-GPTMS-Based Biomaterial: toward a Sustainable Bioprinting of 3D scaffolds for Tissue Engineering Application.

Developing green and nontoxic biomaterials, derived from renewable sources and processable through 3D bioprinting technologies, is an emerging challenge of sustainable tissue engineering. Here, pectin from citrus peels was cross-linked for the first time with (3-glycidyloxypropyl)trimethoxysilane (GPTMS) through a one-pot procedure. Freeze-dried porous pectin sponges, with tunable properties in terms of porosity, water uptake, and compressive modulus, were obtained by controlling GPTMS content. Cell experiments showed that GPTMS did not affect the cytocompatibility of pectin. The addition of GPTMS improved the printability of pectin due to an increase of viscosity and yield stress. Three-dimensional woodpile and complex anatomical-shaped scaffolds with interconnected micro- and macropores were, therefore, bioprinted without the use of any additional support material. These results show the great potential of using pectin cross-linked with GPTMS as biomaterial ink to fabricate patient-specific scaffolds, which could be used to promote tissue regeneration in vivo.

Polyethyleneimine-modified porous aromatic framework and silane coupling agent grafted graphene oxide composite materials for determination of phenolic acids in Chinese Wolfberry drink by HPLC.

A simple method for the determination of phenolic acids in Chinese Wolfberry drink based on polyethyleneimine modified porous aromatic framework and graphene oxide composite sorbent for pipette-tip solid-phase extraction was developed. Porous aromatic framework and raphene oxide composite materials were grafted by silane coupling agent (3-Chloropropyl)-trimethoxysilane. The modified materials were characterized by five kinds of characterization. Experimental results showed that the prepared p-phenylenediamine, cyanuric chloride, and graphene oxide composite material had a loose structure combined with the framework which improved hydrophobicity, and polyethyleneimine to increase the selectivity with the targets. The parameters of the pipette-tip solid-phase extraction procedure including the amount of sorbents, volumes and types of washing solvents and elution solvents were optimized to achieve optimal extraction efficiency. Good linearity of best material was achieved in the range of 0.1-400 µg/mL with correlation coefficient of chlorogenic acid (0.9994), caffeic acid (0.9997), and ferulic acid (0.9998). Recoveries between 93.5 and 102.3% were obtained at three spiked levels with relative standard deviation ≤3.1%. The proposed method was successfully applied for the determination of phenolic acids in Chinese Wolfberry drink sample.

Interfacial separation of concentrated dye mixtures from solution with environmentally compatible nitrogenous-silane nanoparticles modified with Helianthus annuus husk extract.

The capacity of an adsorbent to bind and remove dye from solution greatly depends on the type of functionalization present on the nanoparticles surface, and its interaction with the dye molecules. Within this study, nitrogenous silane nanoparticles were hydrothermally synthesized resulting in the formation of rapid and highly efficient adsorbents for concentrated mixed dyes. The amorphous silane nanoparticles exhibited a monolayer based mechanism of mixed dye adsorption with removal capacities between 416.67 and 714.29 mg/g of adsorbent. Dye removal was predominantly due to the electrostatic attraction between the positively charged silane nanoparticles (13.22-8.20 mV) and the negatively charged dye molecules (-54.23 mV). Addition of H. annuus extract during synthesis resulted in three times the surface area and 10 times increased pore volume compared to the positive control. XPS analysis showed that silane treatments had various nitrogen containing functionalities at their surface responsible for binding dye. The weak colloidal stability of silane particles (13.22-8.20 mV) was disrupted following dye binding, resulting in their rapid coagulation and flocculation which facilitated the separation of bound dye molecules from solution. The suitability for environmental applications using these treatments was supported by a bacterial viability assay showing >90% cell viability in treated dye supernatants.

Acrylamide-Modified 3-Aminopropyltriethoxysilanes Hybrid Monomer for Highly Selective Imprinting Recognition of Theophylline.

The hybrid monomer synthesized with 3-aminopropyltriethoxysilanes and acrylamide was applied for synthesis of molecularly imprinting polymers, and the obtained polymers were used as sorbent in solid-phase extraction for purification of theophylline (THP) in green tea. The static adsorption curves showed better molecular recognition ability and binding capability of the polymers for the target. On the optimized condition, a method was developed for increasing extraction of THP with satisfactory recovery of 93.7%. Good calibration linearity obtained in a range of 5-500 µg·mL-1. The recoveries at three spiked levels ranged from 86.7% to 100.7% with relative standard deviations ≤6.6% (n = 3). The result showed that the obtained polymers exhibited highly selective imprinting recognition to the analyte, and the number of templates was an important factor affecting the selective recognition ability of polymers. The proposed method with hybrid monomer imprinting polymers was successfully applied for purification of THP in green tea.

Indocyanine green loaded APTMS coated SPIONs for dual phototherapy of cancer.

Superparamagnetic iron oxide nanoparticles (SPIONs) have been recently recognized as highly efficient photothermal therapy (PTT) agents. Here, we demonstrate, for the first time to our knowledge, dose and laser intensity dependent PTT potential of small, spherical, 3-aminopropyltrimethoxysilane coated cationic superparamagnetic iron oxide nanoparticles (APTMS@SPIONs) in aqueous solutions upon irradiation at 795 nm. Indocyanine green (ICG) which has been recently used for photodynamic therapy (PDT), was loaded to APTMS@SPIONs to improve the stability of ICG and to achieve an effective mild PTT and PDT (dual therapy) combination for synergistic therapeutic effect on cancer cells via a single laser treatment in the near infrared (NIR). Neither APTMS@SPIONs nor ICG-APTMS@SPIONs showed dark toxicity on MCF7 breast and HT29 colon cancer cell lines. A safe laser procedure was determined as 10 min irradiation at 795 nm with 1.8 W/cm2 of laser intensity, at which APTMS@SPION did not cause a significant cell death. However, free ICG reduced cell viability at and above 10 µg/ml under these conditions along with generation of reactive oxygen species (ROS), more effectively in MCF7. ICG-APTMS@SPION treated cells showed 2-fold increase in ROS generation and near complete cell death at and below 5 µg/ml ICG dose, even in less sensitive HT29 cells after a single laser treatment at NIR, which would be safe for the healthy tissue and provide a longer penetration depth. Besides, both components can be utilized for diagnosis and the overall composition may be used for optical-image guided phototherapy in the NIR region.