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Biocompatible inorganic nano- and microcarriers can be suitable candidates for protein delivery. This study demonstrates facile methods of functionalization by using nanoscale linker molecules to change the protein adsorption capacity of hydroxyapatite (HA) powder. The adsorption capacity of bovine serum albumin as a model protein has been studied with respect to the surface modifications. The selected linker molecules (lysine, arginine, and phosphoserine) can influence the adsorption capacity by changing the electrostatic nature of the HA surface. Qualitative and quantitative analyses of linker-molecule interactions with the HA surface have been performed by using NMR spectroscopy, zeta-potential measurements, X-ray photoelectron spectroscopy, and thermogravimetric analyses. Additionally, correlations to theoretical isotherm models have been calculated with respect to Langmuir and Freundlich isotherms. Lysine and arginine increased the protein adsorption, whereas phosphoserine reduced the protein adsorption. The results show that the adsorption capacity can be controlled with different functionalization, depending on the protein-carrier selections under consideration. The scientific knowledge acquired from this study can be applied in various biotechnological applications that involve biomolecule-inorganic material interfaces.
Assuntos
Arginina/química , Durapatita/química , Lisina/química , Nanopartículas/química , Fosfosserina/química , Adsorção , Animais , Arginina/metabolismo , Bovinos , Durapatita/metabolismo , Lisina/metabolismo , Fosfosserina/metabolismo , Espectroscopia Fotoeletrônica , Propriedades de SuperfícieRESUMO
Although platinum (Pt) is a rare and very expensive material, Pt counter electrodes are still very commonly used for reaching high efficiencies in dye-sensitized solar cells (DSCs). The use of alternative cheaper catalyst materials did not yet yield equivalent efficiencies. In this work, we tried to understand how to reduce the amount of deposited Pt-material and simultaneously deliver higher DSC performances. We systematically compared the properties of Pt-counter electrodes prepared by simple solution deposition methods such as spray-coating, dip-coating, brushing with reference to the Pt-electrodes prepared by sputtering onto fluorine doped-tin oxides (FTOs). The morphological and structural characterizations of the deposited Pt-layers were performed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The composition of Pt-material was quantified using SEM electron dispersive X-ray (EDX) mapping measurements which were further compared with optical transmission measurements. Also contact angle and sheet resistance measurements were performed. By taking Pt-layers composition, morphology and structural factors into account, 9.16% efficient N3 dye based DSCs were assembled. The DSCs were subjected to various opto-electrical characterization techniques like current-voltage (I-V), external quantum efficiency (EQE), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and transient photo voltage (TPV) measurements. The obtained experimental data suggest that the Pt counter electrodes prepared by solution deposition methods can also reach high DSC device performances with a consumption of very little amount of Pt material as compared with sputtered Pt-layers. This process also proves that higher DSC performances are not limited to the usage of sputtered Pt-layer as counter electrode.
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In pharmaceutical applications, the porous particles of organic compounds can improve the efficiency of drug delivery, for example into the pulmonary system. We report on the successful preparation of macroporous spherical granules of mannitol using a spray-drying process using polystyrene (PS) beads of ~340 nm diameter as a sacrificial templating agent. An FDA-approved solvent (ethyl acetate) was used to dissolve the PS beads. A combination of infrared spectroscopy and thermogravimetry analysis proved the efficiency of the etching process, provided that enough PS beads were exposed at the granule surface and formed an interconnected network. Using a lab-scale spray dryer and a constant concentration of PS beads, we observed similar granule sizes (~1-3 microns) and different porosity distributions for the mannitol/PS mass ratio ranging from 10:1 to 1:2. When transferred to a pilot-scale spray dryer, the 1:1 mannitol/PS composition resulted in different distributions of granule size and porosity depending on the atomization configuration (two-fluid or rotary nozzle). In all cases, the presence of PS beads in the spray-drying feedstock was found to favor the formation of the α mannitol polymorph and to lead to a small decrease in the mannitol decomposition temperature when heating in an inert atmosphere.
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Very uniform and well shaped Mn3O4 nano-octahedra are synthesized using a simple hydrothermal method under the help of polyethylene glycol (PEG200) as a reductant and shape-directing agent. The nano-octahedra formation mechanism is monitored. The shape and crystal orientation of the nanoparticles is reconstructed by scanning electron microscopy and electron tomography, which reveals that the nano-octahedra only selectively expose {101} facets at the external surfaces. The magnetic testing demonstrates that the Mn3O4 nano-octahedra exhibit anomalous magnetic properties: the Mn3O4 nano-octahedra around 150 nm show a similar Curie temperature and blocking temperature to Mn3O4 nanoparticles with 10 nm size because of the vertical axis of [001] plane and the exposed {101} facets. With these Mn3O4 nano-octahedra as a catalyst, the photodecomposition of rhodamine B is evaluated and it is found that the photodecomposition activity of Mn3O4 nano-octahedra is much superior to that of commercial Mn3O4 powders. The anomalous magnetic properties and high superior photodecomposition activity of well shaped Mn3O4 nano-octahedra should be related to the special shape of the nanoparticles and the abundantly exposed {101} facets at the external surfaces. Therefore, the shape preference can largely broaden the application of the Mn3O4 nano-octahedra.
Assuntos
Magnetismo , Compostos de Manganês/química , Nanoestruturas/química , Nanotecnologia/métodos , Óxidos/química , Fotoquímica/métodos , Microscopia de Força Atômica , Microscopia Eletrônica de Transmissão , Nanoestruturas/ultraestrutura , Polietilenoglicóis/química , Rodaminas/químicaRESUMO
Monolayers of colloidal spheres are used as masks in nanosphere lithography (NSL) for the selective deposition of nanostructured layers. Several methods exist for the formation of self-organized particle monolayers, among which spin coating appears to be very promising. However, a spin coating process is defined by several parameters like several ramps, rotation speeds, and durations. All parameters influence the spreading and drying of the droplet containing the particles. Moreover, scientists are confronted with the formation of numerous defects in spin coated layers, limiting well-ordered areas to a few micrometers squared. So far, empiricism has mainly ruled the world of nanoparticle self-organization by spin coating, and much of the literature is experimentally based. Therefore, the development of experimental protocols to control the ordering of particles is a major goal for further progress in NSL. We applied experimental design to spin coating, to evaluate the efficiency of this method to extract and model the relationships between the experimental parameters and the degree of ordering in the particles monolayers. A set of experiments was generated by the MODDE software and applied to the spin coating of latex suspension (diameter 490 nm). We calculated the ordering by a homemade image analysis tool. The results of partial least squares (PLS) modeling show that the proposed mathematical model only fits data from strictly monolayers but is not predictive for new sets of parameters. We submitted the data to principal component analysis (PCA) that was able to explain 91% of the results when based on strictly monolayered samples. PCA shows that the ordering was positively correlated to the ramp time and negatively correlated to the first rotation speed. We obtain large defect-free domains with the best set of parameters tested in this study. This protocol leads to areas of 200 µm(2), which has never been reported so far.
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For many opto-electronic applications, F:SnO2 materials must benefit from high transparency, high conductivity, and high mechanical strength even after quenching. The purpose of this study was to investigate the influence of quenching on the opto-electronic properties of the F:SnO2 layers synthesized at high temperature on Si x C y O-coated soda-lime glass by atmospheric chemical vapor deposition. The morphology, structure, and composition of the layers were studied before and after quenching in air- and oxygen-rich atmospheres at 670 °C. The free carrier concentration was reduced by oxygen vacancy (VO) passivation, as well as by F and Na diffusion, with all effects scaling up with quenching time in air. The transmittance also decreased with quenching time as Na impurities acted as absorption and electron recombination centers. In an oxygen-rich atmosphere, the VO passivation was even more emphasized, with however a moderate contribution to conductivity loss. The F:SnO2 layer microstructure and composition were rather fringed through high-temperature deposition. The almost invariable free carrier concentration and transmittance of the F:SnO2 samples quenched in O2 versus air were related to a moderation in Na diffusion. For long quenching times (>20 min) in air, Na and F diffusion prevailed explaining the conductivity drop.
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A hydrothermal synthesis route was used to synthesize iron(III) phosphate hydroxide hydrate-carbon nanotube composites. Carbon nanotubes (CNT) were mixed in solution with Fe1.19(PO4)(OH)0.57(H2O)0.43 (FPHH) precursors for one-pot hydrothermal reaction leading to the FPHH/CNT composite. This produces a highly electronic conductive material to be used as a cathode material for Li-ion battery. The galvanostatic cycling analysis shows that the material delivers a specific capacity of 160 mAh g-1 at 0.2 C (0.2 Li per fu in 1 h), slightly decreasing with increasing current density. A high charge-discharge cyclability is observed, showing that a capacity of 120 mAh g-1 at 1 C is maintained after 500 cycles. This may be attributed to the microspherical morphology of the particles and electronic percolation due to CNT but also to the unusual insertion mechanism resulting from the peculiar structure of FPHH formed by chains of partially occupied FeO6 octahedra connected by PO4 tetrahedra. The mechanism of the first discharge-charge cycle was investigated by combining operando X-ray diffraction and 57Fe Mössbauer spectroscopy. FPHH undergoes a monophasic reaction with up to 10% volume changes based on the Fe3+/Fe2+ redox process. However, the variations of the FPHH lattice parameters and the 57Fe quadrupole splitting distributions during the Li insertion-deinsertion process show a two-step behavior. We propose that such mechanism could be due to the existence of different types of vacant sites in FPHH, including vacant "octahedral" sites (Fe vacancies) that improve diffusion of Li by connecting the one-dimensional channels.
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The surface modification of lamellar silica prepared by liquid crystal templating has been investigated. Two hydrophilic surface modifier agents, 2-glycidoxypropyltrimethoxysilane and 2-[methoxy(polyethyleneoxy)propyl)]trimethoxysilane, have been tested. Characterizations of the modified silica include thermal analysis, (13)C and (29)Si solid state NMR, transmission electron microscopy (TEM) and X-ray diffraction (XRD). The different characterizations confirmed the preservation of the lamellar morphology and the successful surface modification with both silanes along with the template elimination. The results also indicate that the structure and length of the silanes influence the final lamellar organization as well as the grafting yields and mechanisms.
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The structure of the thermoelectric lamellar misfit cobalt oxide [Bi0.84CaO2]2[CoO2]1.69 has been refined using single crystal X-ray diffraction data. Using the four dimensional superspace formalism for aperiodic structures, the superspace group is confirmed P2/m(0delta1/2) (a1 = 4.9069(4), b1 = 4.7135(7), b2 = 2.8256(4), c1 = 14.668(5) A, beta1 = 93.32(1) degrees). The modulated displacements and site occupancies have been refined and are both compatible with the misfit character of the structure, and with a longitudinal modulation of the Bi-O layers of the structure. This modulation is similar to the corresponding one in the related Sr phase [Bi0.87SrO2]2[CoO2]1.82, but now oriented in the orthogonal direction. Because its incommensurate wavelength is locked with the aperiodicity of the misfit structure, it is possible to distinguish between the modulation parameters induced by the accommodation of both subsystems and those related to the longitudinal modulation of the Bi-O layers. In this original structure, two independent aperiodic phenomena coexist in an single crystallographic direction. A particular attention has been paid to the structural configuration of the CoO2 layer, in relation with other similar phases. The thermoelectric properties are probably directly related to the specific distortion of the compressed layer, but the different measured values for the Seebeck coefficient cannot be related to a significant modification of the CoO6 octahedra.
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The biomineralization of otoliths results mainly from the release of soluble Ca(2+), which is in turn precipitated as CaCO(3) crystals. In some Carapidae, sagittae sections have been shown to reveal a three-dimensional asymmetry with a nucleus close to the sulcal side, an unusual position. This study seeks to understand otolith formation in Carapus boraborensis. The unusual shape of the otolith is partly explained by the distribution of the epithelium cells, and particularly the sensory epithelium. Experimental evidence shows for the first time that aragonite growth takes place along the c-axis. These aragonite needles present two different habits. On the sulcal side is found the acicular form resulting from rapid growth during a short period of time. On the anti-sulcal side, the prismatic form seen there is due to a slower growth speed over longer periods. The otolith surface was observed each hour during a period of 24h in fishes reared in similar conditions. This allowed for the first time the direct observation on the otolith surface of the deposition of the two layers (L-zone and D-zone). In C. boraborensis, the organic-rich layer (D-zone) develops during the day, whereas the CaCO(3) layer (L-zone) seems to be deposited during the night.