We use molecular dynamics simulations to study the diffusion of water inside deformed carbon nanotubes with different degrees of eccentricity at 300 K. We found a water structural transition between tubular-like to single-file for (7,7) nanotubes associated with change from a high to low mobility regimes. Water is frozen when confined in a perfect (9,9) nanotube and it becomes liquid if such a nanotube is deformed above a certain threshold. Water diffusion enhancement (suppression) is related to a reduction (increase) in the number of hydrogen bonds. This suggests that the shape of the nanotube is an important ingredient when considering the dynamical and structural properties of confined water.
The addition of propolis extract (PE) to the glass ionomer results in an adhesive material for restorative treatment, with interesting properties mainly due to the flavonoids contained in the propolis extract. However, no study of the flavonoid release profile in these materials was reported. This work studies the flavonoid release profile in such materials aiming to contribute to the future synthesis of optimized devices adept to prolong the efficacy of the drug. The study involved the synthesis and study of the physicochemical, antibacterial and mechanical properties of glass ionomer cement (GIC) and glass-ionomer-propolis composites (GIC-PE). The samples were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analyses. The released concentration of flavonoids, the antimicrobial activity and the compressive strength were also evaluated. Antimicrobial activity was assessed against Streptococcus mutans, Streptococcus salivarius, and Candida albicans, common pathogens in the mouth. The results indicate that the antibacterial activity of GIC-PE samples is closely correlated with the release of flavonoids. The method used to prepare the composite GIC-PE leads to an initial drug delivery burst effect able to diminish partially the population of bacteria tested. The mechanical properties and thermal stability of GIC-PE are higher than those of the GIC and are clearly related to its microstructure. This study is clinically significant because the addition of propolis extract (PE) to the GIC resulted in a novel differentiated product with enhanced mechanical and antimicrobial properties compared to the GIC.
We employed PBE and BLYP semi-local functionals and the van der Waals density functional of Dion et al. (2004) (vdW-DF) to investigate structural properties of liquid acetonitrile and methanol. Among those functionals the vdW-DF is the only one that correctly predicts energy minima in inter-molecular interactions between acetonitrile molecules. We found that van der Waals interactions have a negligible effect on H-bonds in methanol chains. However, it significantly increases chain packing resulting in a more dense liquid in comparison to the other two functionals. The overall trend is that the vdW-DF tends to overestimate density and bulk modulus, meanwhile the semi-local functionals tend to underestimate density. Thus, van der Waals interactions play an important role in the properties of liquids in which much stronger dipole-dipole interactions are present.
Calcium phosphates are suggested as a CO2 adsorbent via pressure swing adsorption. Amorphous calcium phosphate (ACP) and biphasic calcium phosphate (BCP) (composed of hydroxyapatite and beta-tricalcium phosphate) were investigated for the capture/immobilization of the gas. A fluidized bed was set up to assess the levels of CO2 adsorption by ACP and BCP. A gaseous mixture was synthesized, mimicking the conditions for possible industrial use. The results show a significant reduction in CO2 concentrations. Using DFT calculations, we show that CO2 adsorption increases the stability by reducing the surface energy. The energies involved and preferential adsorption sites were also theoretically predicted.
Phenazine derivative molecules were studied using steady state and time resolved fluorescence techniques and demonstrated to lead to strong formation of aggregated species, identified as dimers by time dependent density functional theory calculations. Blended films in a matrix of Zeonex®, produced at different concentrations, showed different contributions of dimer and monomer emissions in a prompt time frame, e.g. less than 50 ns. In contrast, the phosphorescence (e.g. emission from the triplet state) shows no significant effect on dimer formation, although strong dependence of the phosphorescence intensity on concentration is observed, leading to phosphorescence being quenched at higher concentration.
Optical microscopy has been one of the most important tools for visualizing biological samples since the seventeenth century. Recently, with the advances in femtosecond laser technology, all the nonlinear optical processes have now been included as optical microscopy methods, and second harmonic generation (SHG) microscopy has emerged as a powerful new optical imaging tool with applications in medicine and biology. Here we use SHG microscopy to obtain images of 76 prostate biopsies on histological slides. Multiple samples from the excised prostates of patients who underwent a radical prostatectomy were evaluated. The samples were collected from prostate positions as in needle biopsy procedures. The results show the collagen fiber architecture among malignant acini, and analysis of the fiber orientation in the images reveals that the collagen fibers become more aligned at higher malignancy grades. Furthermore, we find that the degree of fiber alignment correlates directly with the Gleason patterns.
The combined use of the microcapillary cell (MEC) and scanning vibrating electrode technique (SVET) and low-angle cross sections was employed to elucidate the role of each coating region on the protection of the cut-edge corrosion of galvanized steels. Different compounds are involved in the blocking action of the corrosion products: Zincite (ZnO) on the steel substrate, hydrozincite (Zn5(OH)6(CO3)2) at the coating/steel interface, and Simonkolleite (Zn5(OH)8Cl2) and ZnO on the different coating regions in different proportions. The coating surface is also active at the initial stage and during long-term protection and thus, must be considered in experimental simulation of the cut-edge corrosion.
The use of chitosan functionalized silica for benznidazole delivery in the treatment of neglected disease such as Chagas disease is one of the forms not yet explored, but with great potential for this therapy, as little is known about nanoformulations for the treatment of Chagas disease. In this work, we used chitosan-succinate covalently attached to the surface pore of MSNs to act as anchor for benznidazole as a delivery system. The samples were characterized structurally and chemically with multiple techniques. The applicability of functionalized MSNs as platforms for benznidazole delivery into T. cruzi parasites was assessed. The results demonstrate that the proposed system is a potential promising nanoplatform for drug and gene delivery targeting neglected diseases such as Chagas disease.
Synthetic polymers are made up of repeated monomeric units, and this gives them a very versatile appearance, making them useful in many areas of science. One is the pharmaceutical, which correlates the properties of the polymer with the active principle, so they can be used as an excipient or in the controlled release system. The PMMA-g-PEG4000 has characteristics derived from its precursors, that are pharmacologically active. When we incorporate drugs into this structure, the polymer can act on the controlled release, lessening the toxic character of the drug and producing fewer side effects. In this work, incorporations of the drug indomethacin were made in the PMMA-g-PEG copolymer and derivatives (PMMA-g-PEG4000 ETIL and PMMA-g-PEG4000 ACET). The samples were characterized by infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM), thermogravimetric analysis (TGA), and atomic force microscopy (AFM) measurements. For each sample, the controlled release was performed in a total time of 4 h and the efficiency of the modified structures was verified.
Abstract Isoxazoles have well established biological activities but, have been underexplored as synthetic intermediates for applications in materials science. The aims of this work are to synthesis a novel isoxazole and analyze its structural and photophysical properties for application in electronic organic materials. The novel bis (phenylisoxazolyl) benzene compound was synthesized in four steps and characterized by NMR, high resolution mass spectrometry, differential thermal analysis, infrared spectroscopy, cyclic voltammetry, ultraviolet–visible spectroscopy, fluorescence spectroscopy, \DFT\ and \TDDFT\ calculations. The molecule presented optical absorption in the ultraviolet region (from 290 nm to 330 nm), with maximum absorption length centered at 306 nm. The molar extinction coefficients (ε), fluorescence emission spectra and quantum efficiencies in chloroform and dimethylformamide solution were determined. Cyclic voltammetry analysis was carried out for estimating the \HOMO\ energy level and these properties make it desirable material for photovoltaic device applications. Finally, the excited-state properties of present compound were calculated by time-dependent density functional theory (TDDFT).
In the present work, we use atomic force microscopy nanomanipulation of 2D-material standing folds to investigate their mechanical deformation. Using graphene, h-BN and talc nanoscale wrinkles as testbeds, universal force–strain pathways are clearly uncovered and well-accounted for by an analytical model. Such universality further enables the investigation of each fold bending stiffness κ as a function of its characteristic height h 0 . We observe a more than tenfold increase of κ as h 0 increases in the 10–100 nm range, with power-law behaviors of κ versus h 0 with exponents larger than unity for the three materials. This implies anomalous scaling of the mechanical responses of nano-objects made from these materials.
Abstract In this work, we demonstrate the nanofabrication of monolayer MoS2 islands using local anodic oxidation of few-layer and bulk MoS2 flakes. The nanofabricated islands present true monolayer Raman signal and photoluminescence intensity up to two orders of magnitude larger than that of a pristine monolayer. This technique is robust enough to result in monolayer islands without the need of
meticulously fine-tuning the oxidation process, thus providing a fast and reliable way of creating monolayer regions with enhanced optical properties and with controllable size, shape, and position.
Despite the advanced stage of diamond thin-film technology, with applications ranging from superconductivity to biosensing, the realization of a stable and atomically thick two-dimensional diamond material, named here as diamondene, is still forthcoming. Adding to the outstanding properties of its bulk and thin-film counterparts, diamondene is predicted to be a ferromagnetic semiconductor with spin polarized bands. Here, we provide spectroscopic evidence for the formation of diamondene by performing Raman spectroscopy of double-layer graphene under high pressure. The results are explained in terms of a breakdown in the Kohn anomaly associated with the finite size of the remaining graphene sites surrounded by the diamondene matrix. Ab initio calculations and molecular dynamics simulations are employed to clarify the mechanism of diamondene formation, which requires two or more layers of graphene subjected to high pressures in the presence of specific chemical groups such as hydroxyl groups or hydrogens.
Abstract Molecular dynamics (MD) employing the Lennard-Jones (LJ) interaction potential was used to compute the heat capacities of argon at constant volume \CV\ and constant pressure \CP\ near the critical point very close to the asymptotic region. The accurate \MD\ calculation of critical divergences was shown to be related to a careful choice of the cutoff radius rc and the inclusion of long-range corrections in the \LJ\ potential. The computed \CP\ and \CV\ values have very good agreement as compared to available \NIST\ data. Furthermore, values of \CV\ in a range of temperatures for which \NIST\ data is not available could be computed. In the investigated range of temperatures, both \CP\ and \CV\ \MD\ results were fitted to a simple mathematical expression based on an empirical model that describes the critical effects when the asymptotic models are not appropriate. The present approach is of general applicability and robust to compute thermophysical properties of fluids in the near-critical region.