Effect of the Electric Field on the Biomineralization of Collagen.

Collagen/hydroxyapatite hybrids are promising biomimetic materials that can replace or temporarily substitute bone tissues. The process of biomineralization was carried out through a double diffusion system. The methodological principle consisted in applying an electric field on the incubation medium to promote the opposite migration of ions into collagen membranes to form hydroxyapatite (HA) on the collagen membrane. Two physically separated solutions were used for the incubation medium, one rich in phosphate ions and the other in calcium ions, and their effects were evaluated against the traditional mineralization in Simulated Body Fluid (SBF). Pre-polarization of the organic membranes and the effect of incubation time on the biomineralization process were also assessed by FTIR and Raman spectroscopies.Our results demonstrated that the membrane pre-polarization significantly accelerated the mineralization process on collagen. On the other side, it was found that the application of the electric field influenced the collagen structure and its interactions with the mineral phase. The increment of the mineralization degree enhanced the photoluminescence properties of the collagen/HA materials, while the conductivity and the dielectric constant were reduced. These results might provide a useful approach for future applications in manufacturing biomimetic bone-like materials.

Enhanced Chitosan Photoluminescence by Incorporation of Lithium Perchlorate.

An improvement in chitosan film photoluminescence was observed after adding LiClO4. FTIR spectra, XPS, DFT calculations, and XRD measurements show an alteration of the H-bonds and an increase in the amorphous character of chitosan. PL spectra display a growth in intensity in the visible region along with the incorporation of lithium, signaling a possible rise in the population density of tail states and, consequently, better photon absorption, as observed from UV-vis measurements. A mechanism through aggregation-induced emission effect is proposed to explain the different results. Although this work establishes the relation between structural changes provoked by LiClO4 incorporation and luminescence in the case of chitosan, we expect that the same approach could be generalized to similar polymeric structures.

Photochemical Reduction of Silver Nanoparticles on Diatoms.

In this work, the photochemical reduction method was used at 440 or 540 nm excitation wavelengths to optimize the deposition of silver nanoparticles on the diatom surface as a potential DNA biosensor. The as-synthesized nanocomposites were characterized by ultraviolet-visible spectroscopy (UV-Vis), Fourier transforms infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), fluorescence microscopy, and Raman spectroscopy. Our results revealed a 5.5-fold enhancement in the fluorescence response of the nanocomposite irradiated at 440 nm with DNA. The enhanced sensitivity comes from the optical coupling of the guided-mode resonance of the diatoms and the localized surface plasmon of the silver nanoparticles interacting with the DNA. The advantage of this work involves the use of a low-cost green method to optimize the deposition of plasmonic nanoparticles on diatoms as an alternative fabrication method for fluorescent biosensors.

Electrochemical Sensor for Hydrogen Peroxide Based on Prussian Blue Electrochemically Deposited at the TiO2-ZrO2-Doped Carbon Nanotube Glassy Carbon-Modified Electrode.

In this investigation, a hydrogen peroxide (H2O2) electrochemical sensor was evaluated. Prussian blue (PB) was electrodeposited at a glassy carbon (GC) electrode modified with titanium dioxide- and zirconia-doped functionalized carbon nanotubes (TiO2.ZrO2-fCNTs), obtaining the PB/TiO2.ZrO2-fCNTs/GC-modified electrode. The morphology and structure of the nanostructured material TiO2.ZrO2-fCNTs was characterized by transmission electron microscopy, the specific surface area was determined via Brunauer-Emmett-Teller, X-ray diffraction, thermogravimetric analysis, and Fourier transform infrared spectroscopy. The electrochemical properties were studied by cyclic voltammetry and chronoamperometry. Titania-zirconia nanoparticles (5.0 ± 2.0 nm) with an amorphous structure were directly synthesized on the fCNT walls, aged during periods of 20 days, obtaining a well-dispersed distribution with a high surface area. The results indicated that the TiO2.ZrO2-fCNT-nanostructured material exhibits good electrochemical properties and could be tunable by enhancing the modification conditions and method of synthesis. Covering of the nanotubes with TiO2-ZrO2 nanoparticles is one of the main factors that affected immobilization and sensitivity of the electrochemical biosensor. The electrode modified with TiO2-ZrO2 nanoparticles with the 20-day aging time was superior regarding its reversibility, electric communication, and high sensitivity and improves the immobilization of the PB at the electrode. The fabricated sensor was used in the detection of H2O2 in whey milk samples, presenting a linear relationship from 100 to 1,000 µmol L-1 between H2O2 concentration and the peak current, with a quantification limit (LQ) of 59.78 µmol L-1 and a detection limit (LD) of 17.93 µmol L-1.

Chitosan-collagen-hydroxyapatite membranes for tissue engineering.

Tissue engineering is growing in developing new technologies focused on providing effective solutions to degenerative pathologies that affect different types of connective tissues. The search for biocompatible, bioactive, biodegradable, and multifunctional materials has grown significantly in recent years. Chitosan, calcium phosphates collagen, and their combination as composite materials fulfill the required properties and could result in biostimulation for tissue regeneration. In the present work, the chitosan/collagen/hydroxyapatite membranes were prepared with different concentrations of collagen and hydroxyapatite. Cell adhesion was evaluated by MTS assay for two in vitro models. Additionally, cytotoxicity of the different membranes employing hemolysis of erythrocytes isolated from human blood was carried out. The structure of the membranes was analyzed by X-rays diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermal stability properties by thermogravimetric methods (TGA). The highest cell adhesion after 48 h was obtained for chitosan membranes with the highest hydroxyapatite and collagen content. All composite membranes showed good cell adhesion and low cytotoxicity, suggesting that these materials have a significant potential to be used as biomaterials for tissue engineering. Graphical abstract.

Simultaneous quantification of Cd(II) and Pb(II) in surface marine sediments using Ag-Hg and Ag-Bi nanoalloys glassy carbon modified electrodes.

The evaluation of glassy carbon (GC) electrodes modified with a Nafion (Nf) film and doped with nanoalloys (Nys) deposits of Ag-Hg and Ag-Bi and their application to determination of Cd (II) and Pb(II) in marine sediments, is described. Deposited Ag-Hg and AgBi Nys have a size of approximately ~80 nm dispersed and embedded inside the booths of the Nf net, while other of them remained on Nf net surface. For the AgBiNysNf-GC electrode, a detection limit (DL), 3 s criterion, slightly higher than for the AgHgNysNf-GC modified electrode was obtained. Accuracy of measurements was asserted by comparison with quantification of Cd and Pb in three sets of marine sediments samples previously analyzed by inductively coupled plasma optical emission spectroscopy (ICP-OES). The values of the standard deviation and the coefficients of variation are very low, and also comparable between the different determinations.

Diatoms decorated with gold nanoparticles by In-situ and Ex-situ methods for in vitro gentamicin release.

The use of natural diatoms is currently a topic of interest for therapeutic applications due to its facilities, low cost, and biocompatibility. Here, we report the chemical modification of diatoms Aulacoseria genus microalgae-derived biosilica from Guayllabamba - Ecuador decorated with gold nanoparticles by In-situ and Ex-situ methods to study the in vitro gentamicin loading and release properties in simulated body fluid (SBF). Successful decoration of the diatoms and loaded with gentamicin was confirmed using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Raman spectroscopy and Fluorescence Microscopy. We follow the In-vitro drug release by using Ultraviolet-Visible Spectroscopy (UV-vis). Our results revealed that diatoms decorated with gold nanoparticles using the Ex-situ method (Au/CTAB-Diatom) showed a faster release reaching a maximum of 93% in 10 days and a lower loading rate, while the samples decorated by the In-situ method presented longer and slower release behavior. Fluorescence properties were enhanced after the gentamicin loaded. The advantage of this work is the control of the structural and optical properties of diatoms decorated with gold nanoparticles for the gentamicin drug delivery.

Optimized and scalable synthesis of magnetic nanoparticles for RNA extraction in response to developing countries' needs in the detection and control of SARS-CoV-2.

Ecuador is one of the most affected countries, with the coronavirus disease 2019 (COVID-19) infection, in Latin America derived from an ongoing economic crisis. One of the most important methods for COVID-19 detection is the use of techniques such as real time RT-PCR based on a previous extraction/purification of RNA procedure from nasopharyngeal cells using functionalized magnetic nanoparticles (MNP). This technique allows the processing of ~ 10,000 tests per day in private companies and around hundreds per day at local Universities guaranteeing to reach a wide range of the population. However, the main drawback of this method is the need for specialized MNP with a strong negative charge for the viral RNA extraction to detect the existence of the SARS-CoV-2 virus. Here we present a simplified low cost method to produce 10 g of nanoparticles in 100 mL of solution that was scaled to one litter by parallelizing the process 10 times in just two days and allowing for the possibility of making ~ 50,000 COVID-19 tests. This communication helps in reducing the cost of acquiring MNP for diverse biomolecular applications supporting developing country budgets constraints and chemical availability specially during the COVID-19 International Health Emergency.

Chitosan-polyvinylpyrrolidone CoxFe3-xO4 (0.25 ≤ x ≤ 1) nanoparticles for hyperthermia applications.

Blends of chitosan (CS) and polyvinylpyrrolidone (PVP) with cobalt ferrite nanoparticles (CoFe2O4) have the potential for use in several biomedical applications as drug delivery systems and for hyperthermia applications. Herein, we present a detailed study of the effect of chitosan and PVP on the structural, magnetic and specific absorption rate (SAR) properties of CoxFe3-xO4 (x = 0.25, 0.50, 0.75 and 1.00) as an effective heat nanomediator for hyperthermia. Structural characterization was carried out using X-ray diffraction (XRD), infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Magnetic properties as a function of the Co2+ content were studied using a vibrating sample magnetometer (VSM) at room temperature. Hyperthermia investigations were performed at 454 ±â€¯20 kHz with a magnetic field amplitude of 5.5 mT. CS-PVP coated nanoparticles at x = 1.00 show a maximum SAR of 386 W/g, while bare nanoparticles show a SAR of 270 W/g. The advantage of the designed nanoparticles coated system lies in the fact that the versatile blending of chitosan and PVP enhance the SAR properties for hyperthermia of cobalt ferrite nanoparticles and provide biocompatibility and stability to the samples.

Electrochemical Sensor Based on Prussian Blue Electrochemically Deposited at ZrO2 Doped Carbon Nanotubes Glassy Carbon Modified Electrode.

In this work, a new hydrogen peroxide (H2O2) electrochemical sensor was fabricated. Prussian blue (PB) was electrodeposited on a glassy carbon (GC) electrode modified with zirconia doped functionalized carbon nanotubes (ZrO2-fCNTs), (PB/ZrO2-fCNTs/GC). The morphology and structure of the nanostructured system were characterized by scanning and transmission electron microscopy (TEM), atomic force microscopy (AFM), specific surface area, X-ray diffraction (XRD), thermogravimetric analysis (TGA), Raman and Fourier transform infrared (FTIR) spectroscopy. The electrochemical properties were studied by cyclic voltammetry (CV) and chronoamperometry (CA). Zirconia nanocrystallites (6.6 ± 1.8 nm) with cubic crystal structure were directly synthesized on the fCNTs walls, obtaining a well dispersed distribution with a high surface area. The experimental results indicate that the ZrO2-fCNTs nanostructured system exhibits good electrochemical properties and could be tunable by enhancing the modification conditions and method of synthesis. The fabricated sensor could be used to efficiently detect H2O2, presenting a good linear relationship between the H2O2 concentration and the peak current, with quantification limit (LQ) of the 10.91 µmol·L-1 and detection limit (LD) of 3.5913 µmol·L-1.

Peroxide Electrochemical Sensor and Biosensor Based on Nanocomposite of TiO2 Nanoparticle/Multi-Walled Carbon Nanotube Modified Glassy Carbon Electrode.

A hydrogen peroxide (H2O2) sensor and biosensor based on modified multi-walled carbon nanotubes (CNTs) with titanium dioxide (TiO2) nanostructures was designed and evaluated. The construction of the sensor was performed using a glassy carbon (GC) modified electrode with a TiO2-CNT film and Prussian blue (PB) as an electrocalatyzer. The same sensor was also employed as the basis for H2O2 biosensor construction through further modification with horseradish peroxidase (HRP) immobilized at the TiO2-fCNT film. Functionalized CNTs (fCNTs) and modified TiO2-fCNTs were characterized by Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), and X-Ray DifFraction (XRD), confirming the presence of anatase over the fCNTs. Depending on the surface charge, a solvent which optimizes the CNT dispersion was selected: dimethyl formamide (DMF) for fCNTs and sodium dodecylsulfate (SDS) for TiO2-fCNTs. Calculated values for the electron transfer rate constant (ks) were 0.027 s-1 at the PB-fCNT/GC modified electrode and 4.7 × 10-4 s-1 at the PB-TiO2/fCNT/GC electrode, suggesting that, at the PB-TiO2/fCNT/GC modified electrode, the electronic transfer was improved. According to these results, the PB-fCNT/GC electrode exhibited better Detection Limit (LD) and Quantification Limit (LQ) than the PB-TiO2/fCNT/GC electrode for H2O2. However, the PB film was very unstable at the potentials used. Therefore, the PB-TiO2/fCNT/GC modified electrode was considered the best for H2O2 detection in terms of operability. Cyclic Voltammetry (CV) behaviors of the HRP-TiO2/fCNT/GC modified electrodes before and after the chronoamperometric test for H2O2, suggest the high stability of the enzymatic electrode. In comparison with other HRP/fCNT-based electrochemical biosensors previously described in the literature, the HRP-fCNTs/GC modified electrode did not show an electroanalytical response toward H2O2.

Infuence of microstructure in drug release behavior of silica nanocapsules.

Meso- and nanoporous structures are adequate matrices for controlled drug delivery systems, due to their large surface areas and to their bioactive and biocompatibility properties. Mesoporous materials of type SBA-15, synthesized under different pH conditions, and zeolite beta were studied in order to compare the different intrinsic morphological characteristics as pore size, pore connectivity, and pore geometry on the drug loading and release process. These materials were characterized by X-ray diffraction, nitrogen adsorption, scanning and transmission electron microscopy, and calorimetric measurements. Ibuprofen (IBU) was chosen as a model drug for the formulation of controlled-release dosage forms; it was impregnated into these two types of materials by a soaking procedure during different periods. Drug loading and release studies were followed by UV-Vis spectrophotometry. All nano- and mesostructured materials showed a similar loading behavior. It was found that the pore size and Al content strongly influenced the release process. These results suggest that the framework structure and architecture affect the drug adsorption and release properties of these materials. Both materials offer a good potential for a controlled delivery system of ibuprofen.

Novel MoO2/carbon hierarchical nano/microcomposites: synthesis, characterization, solid state transformations and thiophene HDS activity.

Novel MoO(2)/C nano/microcomposites were prepared via a bottom-up approach by hydrothermal carbonization of a solution of glucose as a carbon precursor in the presence of polyoxometalates (POMs: phosphomolybdic acid [H(3)PMo(12)O(40)] and ammonium heptamolybdate tetrahydrate [(NH(4))(6)Mo(7)O(24)]·4H(2)O). The structural characterization by FT-IR, XRPD, SEM and TEM analyses revealed the controlled formation of hierarchical MoO(2)/C composites with different morphologies: strawberry-like, based on carbon microspheres decorated with MoO(2) nanoparticles; MoO(2)/C core-shell composites; and irregular aggregates in combination with ring-like microstructures bearing amorphous Mo species. These composites can be fine-tuned by varying reaction time, glucose/POM ratio and type of POM precursor. Subsequent transformations in the solid state through calcinations of MoO(2)/C core-shell composites in air lead to hollow nanostructured molybdenum trioxide microspheres together with nanorods and plate microcrystals or cauliflower-like composites (MoO(2)/C). In addition, the MoO(2)/C composite undergoes a morphology evolution to urchin-like composites when it is calcined under nitrogen atmosphere (MoO(2)/C-N(2)). The MoO(2)/C strawberry-like and MoO(2)/C-N(2) composites were transformed into Mo carbide and nitride supported on carbon microspheres (Mo(2)C/C, MoN/C, and MoN/C-N(2)). These phases were tested as precursors in thiophene hydrodesulphurization (HDS) at 400 °C, observing the following trend in relation to the thiophene steady-state conversion: MoN/C-N(2) > MoN/C > Mo(2)C/C > MoO(2)/C-N(2) > MoO(2)/C. According to these conversion values, a direct correlation was observed between higher HDS activity and decreasing crystal size as estimated from the Scherrer equation. These results suggest that such composites represent interesting and promising precursors for HDS catalysts, where the activity and stability can be modified either by chemical or structural changes of the composites under different conditions.

Effect of Ca/P ratio and milling material on the mechanochemical preparation of hydroxyapaptite.

The mechanochemical transformation of Ca(OH)(2)-(NH(4))(2)HPO(4) with different Ca/P ratios 1; 1.5; 1.67 and 1.75 was carried out for different periods of time from 10 min to 24 h in a horizontal vibration mill using steel and agate vials and balls. The phase transformations obtained at each milling stage were characterized by X-ray diffraction, infrared spectroscopy and transmission electron microscopy. Complete transformation to hydroxyapatite took place during the first 5 h of milling, for Ca/P ratios 1.5 to 1.7, when milling was carried out with steel vials and balls. The contamination was not significant for the periods of milling studied for both milling media.

Characterization of defects and surface structures in microporous materials by HRTEM, HRSEM, and AFM.

High-resolution transmission (HRTEM) and high-resolution scanning electron microscopy as well as atomic force microscopy (AFM), X-ray diffraction, and electron diffraction were used for studying the zeolites MFI, MEL, and the MFIMEL intergrowth system. All three zeolites consisted of individual particles having a size in the range of approximately 0.5 m to 5 m. The particle habits varied from rather cubelike to almost spherelike with many intermediate habits. Typically, the particles of these three zeolites were assembled by many individual blocks that differed in the dimension from about 25 nm to 140 nm as well as in the shape from very frequently almost rectangular (for MFI, MEL, and MFIMEL) to sometimes roundish or irregular habits (mainly for MFIMEL). An estimate shows that some 104 up to more than 106 densely packed blocks typically may assemble each individual zeolite particle or, related to the corresponding unit cell dimension, about 108 up to 1010 unit cells. The fine surface structure of zeolite particles was terracelike with steps between adjacent terraces typically in the range of 20 nm to 60 nm; the minimum step measured was approximately 4 nm. A detailed study of the surface topography was performed by AFM, detecting organic molecules at the block intersections. The presence of topological defects was observed by HRTEM and electron diffraction.