Microbiological, physicomechanical, and surface evaluation of an experimental self-curing acrylic resin containing halloysite nanotubes doped with chlorhexidine.

OBJECTIVE: The objective was to synthesize halloysite nanotubes loaded with chlorhexidine (HNT/CHX) and evaluate the antimicrobial activity, microhardness, color change, and surface characteristics of an experimental self-curing acrylic resin containing varying concentrations of the synthesized nanomaterial. METHODS: The characterization of HNT/CHX was carried out by calculating incorporation efficiency, morphological and compositional, chemical and thermal evaluations. SAR disks were made containing 0 %, 3 %, 5 %, and 10 % of HNT/CHX. Specimens (n = 3) were immersed in distilled water and spectral measurements were carried out using UV/Vis spectroscopy to evaluate the release of CHX for up to 50 days. The antimicrobial activity of the composite against Candida albicans and Streptococcus mutans was evaluated by disk-diffusion test. Microhardness, color analyses (ΔE), and surface roughness (Ra) (n = 9) were performed before and after 30 days of immersion. Data were analyzed using ANOVA/Bonferroni. {Results.} The incorporation efficiency of CHX into HNT was of 8.15 %. All test groups showed controlled and cumulative CHX release up to 30 or 50 days. Significant antimicrobial activity was verified against both microorganisms (p < 0.001). After the 30-day immersion period, the 10 % HNT/CHX group showed a significant increase in hardness (p < 0.05) and a progressive color change (p < 0.001). At T0, the 5 % and 10 % groups exhibited Ra values similar to the control group (p > 0.05), while at T30, all groups showed similar roughness values (p > 0.05). {Significance.} The modification of a SAR with HNT/CHX provides antimicrobial effect and controlled release of CHX, however, the immediate surface roughness in the 3 % group was compromised when compared to the control group.

Chemical, structural and cytotoxicity characterisation of experimental fluoride-doped calcium phosphates as promising remineralising materials for dental applications.

OBJECTIVES: This study aimed at evaluating the cytotoxicity, chemical and structural properties of experimental fluoride-doped calcium-phosphates as potential remineralising materials for dental applications. METHODS: Experimental calcium phosphates were formulated using ß-tricalcium phosphate, monocalcium phosphate monohydrate, calcium hydroxide, and different concentrations of calcium/sodium fluoride salts [(5 wt%: VSG5F), (10 wt%: VSG10F), (20 wt%: VSG20F)]. A fluoride-free calcium phosphate (VSG) was used as control. Each tested material was immersed in simulated body fluid (SBF), (24 h, 15 and 30 days) to assess their ability to crystallise into apatite-like. Cumulative fluoride release was assayed up to 45 days. Moreover, each powder was placed into a medium containing human dental pulp stem cells (200 mg/mL) and their cytotoxicity was analysed using the 3-(4,5-dimethylthiazol-2-yl)- 2,5-diphenyltetrazolium bromide (MTT) assay (24 h, 48 h and 72 h incubation). These latter results were statistically analysed by ANOVA and Tukey's test (α = 0.05). RESULTS: All the experimental VSG-F materials produced fluoride-containing apatite-like crystals after SBF immersion. VSG20F presented prolonged release of fluoride ions into the storage media (45d). VSG, VSG10F and VSG20F showed a significant cytotoxicity at dilution of 1:1, while at 1:5, only VSG and VSG20F demonstrated a reduction in cell viability. At lower dilutions (1:10, 1:50 and 1:100) all specimens showed no significant toxicity to hDPSCs, but an increase in cell proliferation. SIGNIFICANCE: The experimental fluoride-doped calcium-phosphates are biocompatible and possess a clear ability to evoke fluoride-containing apatite-like crystallisation. Hence, they may be promising remineralising materials for dental applications.

Magnetic solid phase extraction as a nonchromatographic method for the quantification of ultratrace inorganic arsenic in rice by inductively coupled plasma-optical emission spectrometry (ICP OES).

An alternative analytical method was developed for the quantification of inorganic arsenic (iAs) in rice by ICP OES. Iron nanoparticles modified with an organophosphorus compound were used as the solid phase for MSPE of iAs from the plant matrix. The MSPE procedure was performed using 4 mL of a buffer solution with pH 4.0, 20 mg of the nanomaterial, and a 15-min extraction time. The total As (tAs) by ICP OES was also quantified using the same MSPE procedure after solubilization of the samples by a block digester. The accuracy of tAs and iAs quantification was verified using CRM NIST 1568b (97 % and 101 % recovery, respectively). The precision (RSD < 15 %) and LOD and LOQ (1.08 and 3.70 µg kg-1, respectively) of the proposed method were satisfactory. The rice samples had tAs contents between 0.090 and 0.295 mg kg-1 and iAs mass fractions between 0.055 and 0.109 mg kg-1.

Graphene and its derivatives: understanding the main chemical and medicinal chemistry roles for biomedical applications.

Over the past few years, there has been a growing potential use of graphene and its derivatives in several biomedical areas, such as drug delivery systems, biosensors, and imaging systems, especially for having excellent optical, electronic, thermal, and mechanical properties. Therefore, nanomaterials in the graphene family have shown promising results in several areas of science. The different physicochemical properties of graphene and its derivatives guide its biocompatibility and toxicity. Hence, further studies to explain the interactions of these nanomaterials with biological systems are fundamental. This review has shown the applicability of the graphene family in several biomedical modalities, with particular attention for cancer therapy and diagnosis, as a potent theranostic. This ability is derivative from the considerable number of forms that the graphene family can assume. The graphene-based materials biodistribution profile, clearance, toxicity, and cytotoxicity, interacting with biological systems, are discussed here, focusing on its synthesis methodology, physicochemical properties, and production quality. Despite the growing increase in the bioavailability and toxicity studies of graphene and its derivatives, there is still much to be unveiled to develop safe and effective formulations.

Biomedical application of graphitic carbon nitrides: tissue depositionin vivo, induction of reactive oxygen species (ROS) and cell viability in tumor cells.

The urgency for new materials in oncology is immediate. In this study we have developed the g-C3N4, a graphitic-like structure formed by periodically linked tris-s-triazine units. The g-C3N4has been synthesized by a simple and fast thermal process. XRD has shown the formation of the crystalline sheet with a compacted structure. The graphite-like structure and the functional groups have been shown by Raman and FTIR spectroscopy. TEM image and AFM revealed the porous composed of five or six C-N layers stacked. DRS and Photoluminescence analyses confirmed the structure with band gap of 2.87 eV and emission band at 448 nm in different wavelengths excitation conditions. The biological results showed inhibitory effect on cancer cell lines and non-toxic effect in normal cell lines. To the best of our knowledge, this is the first work demonstrating the cytotoxic effects of 2D g-C3N4in a cancer cell line, without any external or synergistic influence. The biodistribution/tissue accumulation showed that g-C3N4present a tendency to accumulation on the lung in the first 2 h, but after 24 h the profile of the biodistribution change and it is found mainly in the liver. Thus, 2D-g-C3N4showed great potential for the treatment of several cancer types.

Redox cycling of copper mediated by hydrazine: efficient catalyst systems for oxidative degradation of rhodamine B.

Catalytic processes based on Fenton-like reactions on the degradation of organic pollutants have been improved by accelerating the redox cycling of metal ions. This work presents, at first, the results obtained for the heterogeneous degradation of rhodamine B (RhB) by copper ferrite (CuFe2O4) in presence of hydrogen peroxide (H2O2) and hydrazine (N2H4) as redox cycle accelerator. Atomic absorption spectroscopy showed small amounts of Cu2+ are leached from ferrite highlighting the influence of the homogeneous catalysis in the whole process. The data obtained for the homogeneous process using Cu2+ in solution containing both N2H4 and H2O2 indicated such system is highly efficient mineralizing 73% of RhB within only 10 min of reaction and having H2O and CO2 as major products. Using tert-butyl alcohol as radical scavenger, it was confirmed hydroxyl radical (HO•) is the active oxidant species regarding the RhB degradation. The homogeneous catalyst was applied to a real sample of textile effluent spiked with RhB and showed reasonable efficiency, although lower than that obtained for the standard solutions of RhB. This result was assigned to the interference of salts in the medium that react with HO• thus acting as radical scavenger.

Non-chromatographic arsenic speciation analyses in wild shrimp (Farfantepenaeus brasiliensis) using functionalized magnetic iron-nanoparticles.

A new iron-magnetic nanomaterial functionalized with organophosphorus compound was used as solid-phase for arsenic speciation analysis in seafood samples by ICP-MS. The procedure was optimized using chemometric tools and the variables pH = 4.0, 15 min extraction time, and 20 mg of mass of material were obtained as the optimum point. The inorganic arsenic (iAs) extracted using nanoparticles presented concentrations between 20 and 100 µg kg-1 in the evaluated samples. The method was validated for accuracy using CRMs DOLT-5 and DORM-4. It was possible to reuse the same magnetic nanomaterial for 6 successive cycles, and we obtained a detection limit of 16.4 ng kg-1. The proposed method is suitable for the use of inorganic speciation of As, presenting good accuracy, precision, relatively low cost, and acquittance to green chemistry principles.

Lipase From Rhizomucor miehei Immobilized on Magnetic Nanoparticles: Performance in Fatty Acid Ethyl Ester (FAEE) Optimized Production by the Taguchi Method.

In this communication, it was evaluated the production of fatty acid ethyl ester (FAAE) from the free fatty acids of babassu oil catalyzed by lipase from Rhizomucor miehei (RML) immobilized on magnetic nanoparticles (MNP) coated with 3-aminopropyltriethoxysilane (APTES), Fe3O4@APTES-RML or RML-MNP for short. MNPs were prepared by co-precipitation coated with 3-aminopropyltriethoxysilane and used as a support to immobilize RML (immobilization yield: 94.7 ± 1.0%; biocatalyst activity: 341.3 ± 1.2 U p -NPB/g), which were also activated with glutaraldehyde and then used to immobilize RML (immobilization yield: 91.9 ± 0.2%; biocatalyst activity: 199.6 ± 3.5 U p -NPB/g). RML-MNP was characterized by X-Ray Powder Diffraction (XRPD), Fourier Transform-Infrared (FTIR) spectroscopy and Scanning Electron Microscope (SEM), proving the incorporation and immobilization of RML on the APTES matrix. In addition, the immobilized biocatalyst presented at 60°C a half-life 16-19 times greater than that of the soluble lipase in the pH range 5-10. RML and RML-MNP showed higher activity at pH 7; the immobilized enzyme was more active than the free enzyme in the pH range (5-10) analyzed. For the production of fatty acid ethyl ester, under optimal conditions [40°C, 6 h, 1:1 (FFAs/alcohol)] determined by the Taguchi method, it was possible to obtain conversion of 81.7 ± 0.7% using 5% of RML-MNP.

A new heterofunctional support for enzyme immobilization: PEI functionalized Fe3O4 MNPs activated with divinyl sulfone. Application in the immobilization of lipase from Thermomyces lanuginosus.

Lipase from Thermomyces lanuginosus (TLL) was immobilized onto a novel heterofunctional support, divinyl sulfone (DVS) superparamagnetic nanoparticles (SPMNs) functionalized with polyethyleneimine (PEI). Particle size and zeta potential measurements, elemental analysis, X-ray powder diffraction, magnetic measurements, and infrared spectroscopy analysis were used to characterize the TLL preparations. At pH 10, it was possible to achieve 100 % of immobilization yield in 1 h. The immobilization pH gives TLL preparations with different stabilities; indeed the TLL preparation immobilized at pH 5.0 was the most stable during the thermal inactivation at all pH values. For the hydrolysis of racemic methyl mandelate, the nanobiocatalysts immobilized at pH 5.0 and blocked with ethylenediamine (EDA) and ethanolamine (ETA) obtained good enantioselectivities (68 % and 72 %, respectively) with high catalytic activities in the reaction medium at pH 7.0. The operational stability of the systems was evaluated in the esterification reaction of benzyl alcohol, obtaining up to 61 % conversion after the seventh reaction cycle. These results show that SPMN@PEI-DVS support is a robust strategy for the easy and rapid recovery of the nanobiocatalyst by applying a magnetic field, showing great potential for industrial applications.

Magnetic Porous Controlled Fe3O4-Chitosan Nanostructure: An Ecofriendly Adsorbent for Efficient Removal of Azo Dyes.

In this work, chitosan/magnetite nanoparticles (ChM) were quickly synthesized according to our previous report based on co-precipitation reaction under ultrasound (US) irradiation. Besides ChM was in-depth structurally characterized, showing a crystalline phase corresponding to magnetite and presenting a spheric morphology, a "nanorod"-type morphology was also obtained after increasing reaction time for eight minutes. Successfully, both morphologies presented a nanoscale range with an average particle size of approximately 5-30 nm, providing a superparamagnetic behavior with saturation magnetization ranging from 44 to 57 emu·g-1. As ChM nanocomposites have shown great versatility considering their properties, we proposed a comparative study using three different amine-based nanoparticles, non-surface-modified and surface-modified, for removal of azo dyes from aqueous solutions. From nitrogen adsorption-desorption isotherm results, the surface-modified ChMs increased the specific surface area and pore size. Additionally, the adsorption of anionic azo dyes (reactive black 5 (RB5) and methyl orange (MO)) on nanocomposites surface was pH-dependent, where surface-modified samples presented a better response under pH 4 and non-modified one under pH 8. Indeed, adsorption capacity results also showed different adsorption mechanisms, molecular size effect and electrostatic attraction, for unmodified and modified ChMs, respectively. Herein, considering all results and nanocomposite-type structure, ChM nanoparticles seem to be a suitable potential alternative for conventional anionic dyes adsorbents, as well as both primary materials source, chitosan and magnetite, are costless and easily supplied.

Ethyl Butyrate Synthesis Catalyzed by Lipases A and B from Candida antarctica Immobilized onto Magnetic Nanoparticles. Improvement of Biocatalysts' Performance under Ultrasonic Irradiation.

The synthesis of ethyl butyrate catalyzed by lipases A (CALA) or B (CALB) from Candida antarctica immobilized onto magnetic nanoparticles (MNP), CALA-MNP and CALB-MNP, respectively, is hereby reported. MNPs were prepared by co-precipitation, functionalized with 3-aminopropyltriethoxysilane, activated with glutaraldehyde, and then used as support to immobilize either CALA or CALB (immobilization yield: 100 ± 1.2% and 57.6 ± 3.8%; biocatalysts activities: 198.3 ± 2.7 Up-NPB/g and 52.9 ± 1.7 Up-NPB/g for CALA-MNP and CALB-MNP, respectively). X-ray diffraction and Raman spectroscopy analysis indicated the production of a magnetic nanomaterial with a diameter of 13.0 nm, whereas Fourier-transform infrared spectroscopy indicated functionalization, activation and enzyme immobilization. To determine the optimum conditions for the synthesis, a four-variable Central Composite Design (CCD) (biocatalyst content, molar ratio, temperature and time) was performed. Under optimized conditions (1:1, 45 °C and 6 h), it was possible to achieve 99.2 ± 0.3% of conversion for CALA-MNP (10 mg) and 97.5 ± 0.8% for CALB-MNP (12.5 mg), which retained approximately 80% of their activity after 10 consecutive cycles of esterification. Under ultrasonic irradiation, similar conversions were achieved but at 4 h of incubation, demonstrating the efficiency of ultrasound technology in the enzymatic synthesis of esters.

Nanomaterials Based on Fe3O4 and Phthalocyanines Derived from Cashew Nut Shell Liquid.

In this work we report the synthesis of new hybrid nanomaterials in the core/shell/shell morphology, consisting of a magnetite core (Fe3O4) and two consecutive layers of oleic acid (OA) and phthalocyanine molecules, the latter derived from cashew nut shell liquid (CNSL). The synthesis of Fe3O4 nanoparticle was performed via co-precipitation procedure, followed by the nanoparticle coating with OA by hydrothermal method. The phthalocyanines anchorage on the Fe3O4/OA core/shell nanomaterial was performed by facile and effective sonication method. The as obtained Fe3O4/OA/phthalocyanine hybrids were investigated by Fourier transform infrared spectroscopy, X-ray diffraction, UV-visible spectroscopy, transmission electron microscopy (TEM), thermogravimetric analysis and magnetic measurements. TEM showed round-shaped nanomaterials with sizes in the range of 12-15 nm. Nanomaterials presented saturation magnetization (Ms) in the 1-16 emu/g and superparamagnetic behavior. Furthermore, it was observed that the thermal stability of the samples was directly affected by the insertion of different transition metals in the ring cavity of the phthalocyanine molecule.

Immobilization of Lipase A from Candida antarctica onto Chitosan-Coated Magnetic Nanoparticles.

In this communication, lipase A from Candida antarctica (CALA) was immobilized by covalent bonding on magnetic nanoparticles coated with chitosan and activated with glutaraldehyde, labelled CALA-MNP, (immobilization parameters: 84.1% ± 1.0 for immobilization yield and 208.0 ± 3.0 U/g ± 1.1 for derivative activity). CALA-MNP biocatalyst was characterized by X-ray Powder Diffraction (XRPD), Fourier Transform Infrared (FTIR) spectroscopy, Thermogravimetry (TG) and Scanning Electron Microscope (SEM), proving the incorporation of magnetite and the immobilization of CALA in the chitosan matrix. Besides, the immobilized biocatalyst showed a half-life 8-11 times higher than that of the soluble enzyme at pH 5-9. CALA showed the highest activity at pH 7, while CALA-MNP presented the highest activity at pH 10. The immobilized enzyme was more active than the free enzyme at all studied pH values, except pH 7.

Chitosan activated with divinyl sulfone: a new heterofunctional support for enzyme immobilization. Application in the immobilization of lipase B from Candida antarctica.

A novel heterofunctional support for enzyme immobilization, chitosan-divinyl sulfone, was assessed in this study. The activation of chitosan with DVS was carried out at three different pHs (10.0, 12.5 and 14.0) and a Candida antarctica Lipase B (CALB) was selected as the model enzyme. After immobilization, the biocatalysts were incubated under alkaline conditions in a buffer to facilitate the multipoint covalent attachment, followed by incubation in ethylenediamine (EDA) aiming at blocking the remaining reactive groups. The highest thermal stability was obtained when pH 10.0 was used during support activation. These results were shown to be better than those obtained when using glutaraldehyde as the support-activating reagent. Subsequently, the immobilization pH was investigated (5.0, 7.0 and 10.0) prior to alkaline incubation, with the highest enzyme stability levels found at pH 10.0. Finally, the selected biocatalyst was used in the hydrolysis of ethyl hexanoate and presented an activity of 14,520.37 U/g of immobilized lipase at pH 5.0. These results show that chitosan activated with divinyl sulfone is a very promising support for enzyme immobilization and the proposed protocol is able to successfully improve enzyme stability.

Biogenic synthesis of multifunctional silver nanoparticles from Rhodotorula glutinis and Rhodotorula mucilaginosa: antifungal, catalytic and cytotoxicity activities.

Silver nanoparticles (AgNPs) have several technological applications and may be synthetized by chemical, physical and biological methods. Biosynthesis using fungi has a wide enzymatic range and it is easy to handle. However, there are few reports of yeasts with biosynthetic ability to produce stable AgNPs. The purpose of this study was to isolate and identify soil yeasts (Rhodotorula glutinis and Rhodotorula mucilaginosa). After this step, the yeasts were used to obtain AgNPs with catalytic and antifungal activity evaluation. Silver Nanoparticles were characterized by UV-Vis, DLS, FTIR, XRD, EDX, SEM, TEM and AFM. The AgNPs produced by R. glutinis and R. mucilaginosa have 15.45 ± 7.94 nm and 13.70 ± 8.21 nm (average ± SD), respectively, when analyzed by TEM. AgNPs showed high catalytic capacity in the degradation of 4-nitrophenol and methylene blue. In addition, AgNPs showed high antifungal activity against Candida parapsilosis and increase the activity of fluconazole (42.2% for R. glutinis and 29.7% for R. mucilaginosa), while the cytotoxicity of AgNPs was only observed at high concentrations. Finally, two yeasts with the ability to produce AgNPs were described and these particles showed multifunctionality and can represent a technological alternative in many different areas with potential applications.

Chitosan-magnetite nanocomposite as a sensing platform to bendiocarb determination.

A novel platform for carbamate-based pesticide quantification using a chitosan/magnetic iron oxide (Chit-Fe3O4) nanocomposite as a glassy carbon electrode (GCE) modifier is shown for an analytical methodology for determination of bendiocarb (BND). The BND oxidation signal using GCE/Chit-Fe3O4 compared with bare GCE was catalyzed, showing a 37.5% of current increase with the peak potential towards less positive values, showing method's increased sensitivity and selectivity. Using square-wave voltammetry (SWV), calibration curves for BND determination were obtained (n = 3), and calculated detection and quantification limits values were 2.09 × 10-6 mol L-1 (466.99 ppb) and 6.97 × 10-6 mol L-1 (1555.91 ppb), respectively. The proposed electroanalytical methodology was successfully applied for BND quantification in natural raw waters without any sample pretreatment, proving that the GCE/Chit-Fe3O4 modified electrode showed great potential for BND determination in complex samples. ᅟ Graphical abstract.

A rare cationic building block that generates a new type of polyhedral network with "cross-linked" pto topology.

A rare 8-connected cationic building block, [Cu2L8(µ-MF6)](2+) (L = pyridyl ligand, M = Si, Ti, Ge, Zr or Sn), enables the formation of a small cubicuboctahedral supramolecular building block, SBB, when complexed by 2,4,6-tris(4-pyridyl)pyridine. The coordination network resulting from fusing the square faces of the SBBs can be described as a pto topology in which half of the square faces are cross-linked by MF6(2-) moieties, and represents the first example of a new 3,5-c topology.

Magnetic nanosystem for cancer therapy using oncocalyxone a, an antitomour secondary metabolite isolated from a Brazilian plant.

This paper describes the investigation and development of a novel magnetic drug delivery nanosystem (labeled as MO-20) for cancer therapy. The drug employed was oncocalyxone A (onco A), which was isolated from Auxemma oncocalyx, an endemic Brazilian plant. It has a series of pharmacological properties: antioxidant, cytotoxic, analgesic, anti-inflammatory, antitumor and antiplatelet. Onco A was associated with magnetite nanoparticles in order to obtain magnetic properties. The components of MO-20 were characterized by XRD, FTIR, TGA, TEM and Magnetization curves. The MO-20 presented a size of about 30 nm and globular morphology. In addition, drug releasing experiments were performed, where it was observed the presence of the anomalous transport. The results found in this work showed the potential of onco A for future applications of the MO-20 as a new magnetic drug release nanosystem for cancer treatment.

Adsorption of polycyclic aromatic hydrocarbons from aqueous solutions by modified periodic mesoporous organosilica.

A novel procedure was developed for the synthesis of a periodic mesoporous organosilica (PMO), which was used to remove polycyclic aromatic hydrocarbons (PAHs) from aqueous solutions. Adsorption equilibrium isotherms and adsorption kinetics experiments were carried out in solutions of PAHs (2-60 mg L(-1)), using the PMO as adsorbent. Adsorption models were used to predict the mechanisms involved. The adsorption kinetics data best fitted the pseudo-first-order kinetic model for naphthalene, and to the pseudo-second-order model for fluorene, fluoranthene, pyrene, and acenaphtene. The intraparticle model was also tested and pointed to the occurrence of such processes in all cases. The isotherm models which best represented the data obtained were the Freundlich model for fluoranthene, pyrene, and fluorene, the Temkin model for naphthalene, and the Redlich-Peterson model for acenaphtene. PAHs showed similar behavior regarding kinetics after 24 h of contact between adsorbent and PAHs. FTIR, XRD, BET, and SEM techniques were used for the characterization of the adsorbent material.

Evaluation of a low-cost adsorbent for removal of toxic metal ions from wastewater of an electroplating factory.

In this study, sugar cane residue or bagasse was used for removal of toxic metal ions from wastewater of an electroplating factory located in northeast Brazil. Prior acid treatment increased the adsorption efficacies in batch wise experiments. The microstructure of the material before and after the treatment was investigated by X-ray diffraction, infrared spectroscopy and scanning electron microscopy. Column operations showed that removals of Cu(2+), Ni(2+) and Zn(2+) from wastewater (in the absence of cyanide) were 95.5%, 96.3.0%, and 97.1%, respectively. Regeneration of the adsorbent obtained in acid indicated that the efficiencies decreased only after the fourth cycle of re-use. Acid-treated sugar cane bagasse can be considered a viable alternative to common methods to remove toxic metal ions from aqueous effluents of electroplating industries.