Mineral matrix deposition of MC3T3-E1 pre-osteoblastic cells exposed to silicocarnotite and nagelschmidtite bioceramics: In vitro comparison to hydroxyapatite.

This work presents the effect of the silicocarnotite (SC) and nagelschmidtite (Nagel) phases on in vitro osteogenesis. The known hydroxyapatite of biological origin (BHAp) was used as a standard of osteoconductive characteristics. The evaluation was carried out in conventional and osteogenic media for comparative purposes to assess the osteogenic ability of the bioceramics. First, the effect of the material on cell viability at 24 h, 7 and 14 days of incubation was evaluated. In addition, cell morphology and attachment on dense bioceramic surfaces were observed by fluorescence microscopy. Specifically, alkaline phosphatase (ALP) activity was evaluated as an osteogenic marker of the early stages of bone cell differentiation. Mineralized extracellular matrix was observed by calcium phosphate deposits and extracellular vesicle formation. Furthermore, cell phenotype determination was confirmed by scanning electron microscope. The results provided relevant information on the cell attachment, proliferation, and osteogenic differentiation processes after 7 and 14 days of incubation. Finally, it was demonstrated that SC and Nagel phases promote cell proliferation and differentiation, while the Nagel phase exhibited a superior osteoconductive behavior and could promote MC3T3-E1 cell differentiation to a higher extent than SC and BHAp, which was reflected in a higher number of deposits in a shorter period for both conventional and osteogenic media.

Interlayer charge transfer in supported and suspended MoS2/Graphene/MoS2 vertical heterostructures.

In this letter, we report on the optical and structural properties of supported and suspended MoS2/Graphene/MoS2 vertical heterostructures using Raman and photoluminescence (PL) spectroscopies. Vertical heterostructures (VH) are formed by multiple wet transfers on micro-sized holes in SiO2/Si substrates, resulting in VH with different configurations. The strong interlayer coupling is confirmed by Raman spectroscopy. Additionally, we observe an enhancement of the PL emission in the three-layer VH (either support or suspended) compared with bare MoS2 or MoS2/Graphene. This suggests the formation of a spatial type-II band alignment assisted by the graphene layer and thus, the operation of the VH as a n++/metal/n junction.

Ligninolytic activity of the Penicillium chrysogenum and Pleurotus ostreatus fungi involved in the biotransformation of synthetic multi-walled carbon nanotubes modify its toxicity.

Multi-walled carbon nanotubes (MWCNTs) are of multidisciplinary scientific interest due to their exceptional physicochemical properties and a broad range of applications. However, they are considered potentially toxic nanoparticles when they accumulate in the environment. Given their ability to oxidize resistant polymers, mycorremediation with lignocellulolytic fungi are suggested as biological alternatives to the mineralization of MWCNTs. Hence, this study involves the ability of two fungi specie to MWCNTs biotransformation by laccase and peroxidases induction and evaluation in vivo of its toxicity using Caenorhabditis elegans worms as a model. Results showed that the fungi Penicillium chrysogenum and Pleurotus ostreatus were capable to grow on media with MWCNTs supplemented with glucose or lignin. Activities of lignin-peroxidase, manganese-peroxidase, and laccase in cultures of both fungi were induced by MWCNTs. Raman, FTIR spectroscopy, HR-TEM, and TGA analyses of the residue from the cultures of both fungi revealed structural modifications on the surface of MWCNTs and its amount diminished, correlating the MWCNTs structural modifications with the laccase-peroxidase activities in the fungal cultures. Results indicate that the degree of toxicity of MWCNTs on the C. elegans model was enhanced by the structure modification associated with the fungal ligninolytic activity. The toxic effect of MWCNTs on the in vivo model of worms reveals the increment of reactive oxygen species as a mechanism of toxicity. Findings indicate that the MWCNTs can be subject in nature to biotransformation processes such as the fungal metabolism, which contribute to modify their toxicity properties on susceptible organisms and contributing to environmental elimination.

Comment on "Investigation on the structure and thermoelectric properties of CuxTe binary compounds" by Shriparna Mukherjee et al., Dalton Trans., 2019, 48, 1040.

The Raman spectra of copper tellurides are nearly unknown. This is due not only to the difficulty in obtaining single-phase specimens, but also to the low inelastic light scattering efficiency of Cu2-xTe. To date, only the Raman spectrum of the vulcanite phase, CuTe, has been both measured and calculated by density functional theory. The authors of the commented work reported the Raman spectra of Cu2Te, Cu1.6Te and Cu1.25Te samples. However, the assignment of the measured modes has been defective and their Raman spectra lack some of the features usually found for copper tellurides.

Dual-doped CdSe:Cu:O films grown by sputtering using CdSe-CuO composite targets.

The effects of the simultaneous incorporation of Cu and O in CdSe films grown by sputtering are presented. The Cu and O contents varied between 1 and 5 at.% in films deposited at 150, 200, 250 and 300 °C. Concentrations of 2, 3, 4 and 5 at.% of CuO in the target promoted the formation of copper selenide clusters immersed within the CdSe:Cu:O host. Energy considerations (enthalpy of formation and bond dissociation energy) were used to discuss the absence of copper oxide and the formation of copper selenide aggregates, as well as the film thickness dependence on the concentration of CuO in the target. The band gap of the films ranged from 1.21 to 2.07 eV, depending upon growth conditions. Significant below-band-gap absorption was observed which was ascribed to the copper selenide micro and nano clusters. Good crystalline quality of the films, for high substrate temperatures, was evidenced through the appearance of overtones of the vibrational longitudinal optic modes detected by Raman micro spectroscopy. It was determined that the electronic properties, optical transmission and electrical conductivity depended on the chemical composition and crystalline structure. This characteristic is relevant because through copper and oxygen co-doping is possible to control these technologically important physical properties of CdSe in a simple and reliable manner.

Crystalline structure, electronic and lattice-dynamics properties of NbTe2.

Layered-structure materials are currently relevant given their quasi-2D nature. Knowledge of their physical properties is currently of major interest. Niobium ditelluride possesses a monoclinic layered-structure with a distortion in the tellurium planes. This structural complexity has hindered the determination of its fundamental physical properties. In this work, NbTe2 crystals were used to elucidate its structural, compositional, electronic and vibrational properties. These findings have been compared with calculations based on density functional theory. The chemical composition and elemental distribution at the nanoscale were obtained through atom probe tomography. Ultraviolet photoelectron spectroscopy allowed the first determination of the work function of NbTe2. Its high value, 5.32 eV, and chemical stability allow foreseeing applications such as contact in optoelectronics. Raman spectra were obtained using different excitation laser lines: 488, 633, and 785 nm. The vibrational frequencies were in agreement with those determined through density functional theory. It was possible to detect a theoretically-predicted, low-frequency, low-intensity Raman active mode not previously observed. The dispersion curves and electronic band structure were calculated, along with their corresponding density of states. The electrical properties, as well as a pseudo-gap in the density of states around the Fermi energy are characteristics proper of a semi metal.

Biological effects of carbon nanotubes generated in forest wildfire ecosystems rich in resinous trees on native plants.

Carbon nanotubes (CNTs) have a broad range of applications and are generally considered human-engineered nanomaterials. However, carbon nanostructures have been found in ice cores and oil wells, suggesting that nature may provide appropriate conditions for CNT synthesis. During forest wildfires, materials such as turpentine and conifer tissues containing iron under high temperatures may create chemical conditions favorable for CNT generation, similar to those in synthetic methods. Here, we show evidence of naturally occurring multiwalled carbon nanotubes (MWCNTs) produced from Pinus oocarpa and Pinus pseudostrobus, following a forest wildfire. The MWCNTs showed an average of 10 walls, with internal diameters of ∼2.5 nm and outer diameters of ∼14.5 nm. To verify whether MWCNT generation during forest wildfires has a biological effect on some characteristic plant species of these ecosystems, germination and development of seedlings were conducted. Results show that the utilization of comparable synthetic MWCNTs increased seed germination rates and the development of Lupinus elegans and Eysenhardtia polystachya, two plants species found in the burned forest ecosystem. The finding provides evidence that supports the generation and possible ecological functions of MWCNTs in nature.

Malfunctioning of the iron-sulfur cluster assembly machinery in Saccharomyces cerevisiae produces oxidative stress via an iron-dependent mechanism, causing dysfunction in respiratory complexes.

Biogenesis and recycling of iron-sulfur (Fe-S) clusters play important roles in the iron homeostasis mechanisms involved in mitochondrial function. In Saccharomyces cerevisiae, the Fe-S clusters are assembled into apoproteins by the iron-sulfur cluster machinery (ISC). The aim of the present study was to determine the effects of ISC gene deletion and consequent iron release under oxidative stress conditions on mitochondrial functionality in S. cerevisiae. Reactive oxygen species (ROS) generation, caused by H2O2, menadione, or ethanol, was associated with a loss of iron homeostasis and exacerbated by ISC system dysfunction. ISC mutants showed increased free Fe2+ content, exacerbated by ROS-inducers, causing an increase in ROS, which was decreased by the addition of an iron chelator. Our study suggests that the increment in free Fe2+ associated with ROS generation may have originated from mitochondria, probably Fe-S cluster proteins, under both normal and oxidative stress conditions, suggesting that Fe-S cluster anabolism is affected. Raman spectroscopy analysis and immunoblotting indicated that in mitochondria from SSQ1 and ISA1 mutants, the content of [Fe-S] centers was decreased, as was formation of Rieske protein-dependent supercomplex III2IV2, but this was not observed in the iron-deficient ATX1 and MRS4 mutants. In addition, the activity of complexes II and IV from the electron transport chain (ETC) was impaired or totally abolished in SSQ1 and ISA1 mutants. These results confirm that the ISC system plays important roles in iron homeostasis, ROS stress, and in assembly of supercomplexes III2IV2 and III2IV1, thus affecting the functionality of the respiratory chain.

Lanthanide(III) complexes with 4,5-bis(diphenylphosphinoyl)-1,2,3-triazolate and the use of 1,10-phenanthroline as auxiliary ligand.

New lanthanide complexes with 4,5-bis(diphenyl)phosphoranyl-1,2,3-triazolate (L(-)), LnL(3).nH(2)O (1-8) and LnL(3)(phen).nH(2)O (9-16) (Ln = La, Ce, Nd, Sm, Eu, Gd, Tb, Er), have been prepared and spectroscopically characterized. The structures of LnL(3).nH(2)O (Ln = La, Ce, Nd, Sm and Gd) were determined by X-ray crystallography. The metal centers exhibit a distorted trigonal dodecahedron coordination environment with two symmetrically O,O-bidentate ligands and one unsymmetrically O,N- ligand attached to the metal; two oxygen atoms from neighboring dimethyl sulfoxide (DMSO) molecules complete the coordination sphere. This unsymmetrical ligand coordination behavior was also identified in solution through (31)P{(1)H} NMR studies. Photoluminescence spectroscopy experiments in CH(2)Cl(2) for both types of complexes containing Eu(III) (6, 14) and Tb(III) (7, 15) exhibit strong characteristic red and green emission bands for Eu(III) and Tb(III), respectively. Furthermore, NdL(3) (phen).5H (2)O (11) displays emission in the near-infrared spectral region ((4)F(3/2) --> (4)F(9/2) at 872 nm and (4)F(3/2) --> (4)F(11/2) at 1073 nm). The complexes containing 1,10-phenantroline exhibit higher quantum yields upon excitation at 267 nm, indicating that this auxiliary ligand promotes the luminescence of the complexes; however, luminescence lifetimes (tau) in this case are shorter than those of the LnL(3).nH(2)O series.