Cobalt oxide nanoparticles on mesoporous MCM-41 and Al-MCM-41 by supercritical CO2 deposition

CoO and Co₃O₄ nanoparticles were uniformly dispersed inside mesoporous MCM-41 and Al-MCM-41 supports using supercritical CO₂ reactive deposition. This method represents a one-pot reproducible procedure that allows the dissolution of the organocobalt precursor and supports impregnation in supercritical CO₂ at 70 °C and 110 bar, followed by the precursor thermal decomposition into cobalt species at 200 °C and 160 bar. By the relative concentration of the cobalt precursor [cobalt (II) bis (η⁵-ciclopentadienil)], the load of cobalt nanoparticles was controlled and then determined by Inductively Coupled Plasma (ICP-OES). The synthesis of CoO and Co₃O₄ species inside the MCM-41 and Al-MCM-41 substrates was confirmed by X-ray Photoelectron (XPS) and Laser Raman Spectroscopies (LRS). By N₂ adsorption and Small Angle X-ray Scattering (SAXS), it was determined that the hexagonal arrangement as well as the surface area and pore size of the substrates changed after the addition of cobalt. By means of X-ray mapping from SEM images, a homogeneous distribution of cobalt nanoparticles was observed inside the mesopores when the cobalt loading was 1 wt.%. In addition, spherical cobalt nanoparticles of average diameter close to 20 nm were detected on the outer surface of MCM-41 and Al-MCM-41 supports when the cobalt content was higher. On the other hand, by Transmission Electron Microscopy (TEM), it was possible to measure the interplanar distance of the crystalline plane of the outer nanoparticles, which was later compared with the theoretical distance values which allowed identifying the CoO and Co₃O₄ phases.     

Contribution of “click chemistry” to the synthesis of antimicrobial aliphatic copolyester

A straightforward strategy is proposed to impart antimicrobial properties to biodegradable poly(oxepan-2-one) (poly(?-caprolactone) or PCL), which is based on the grafting of pendant ammonium salts by “click” chemistry. First, statistical copolymerization of 3-chlorooxepan-2-one (α-chloro-?-caprolactone or αCl?CL) with oxepan-2-one (?-caprolactone or ?CL) was initiated by 2,2-dibutyl-2-stanna-1,3-dioxepane (DSDOP). In a second step, pendant chlorides were converted into azides by reaction with sodium azide (NaN₃). Finally, quaternary ammonium containing alkynes were quantitatively added to the pendant azide groups of PCL by the copper-catalyzed Huisgen's 1,3-dipolar cycloaddition, which is a typical “click” reaction. An alternative two-step strategy based on the cycloaddition of the amine containing alkyne onto the pendant azides, followed by quaternization turned out to be less efficient. The antimicrobial activity was analyzed by the “shaking flask method” in the presence of Escherichia coli (E. coli).     

Retention of pesticides in soil columns modified in situ and ex situ with a cationic surfactant

A study of the effect of a clayey soil modified in situ and ex situ with the cationic surfactant octadecyltrimethylammonium bromide (ODTMA), on the retention of linuron, atrazine and metalaxyl was carried out. Leaching of these compounds was studied in columns of a natural clayey soil and the same clayey soil modified by direct injection of the surfactant in situ, and in columns of a natural sandy soil and the same sandy soil modified by intercalation of a barrier of the clayey soil saturated ex situ with the surfactant. Breakthrough curves indicated the total immobilization of linuron in modified soils and a decrease in the leaching kinetics of atrazine and metalaxyl compared to what was obtained in the natural soil. The results indicate the use of the clayey soil modified in situ or ex situ with the surfactant ODTMA could be of interest in the immobilization of pesticides of different hydrophobicities.     

Is presence a technology issue? Some insights from cognitive sciences

The International Society of Presence Research, defines “presence” (a shortened version of the term “telepresence”) as a “psychological state in which even though part or all of an individual’s current experience is generated by and/or filtered through human-made technology, part or all of the individual’s perception fails to accurately acknowledge the role of the technology in the experience” (ISPR 2000, The concept of presence: explication statement. Accessed 15 Jan 2009). In this article, we will draw on the recent outcomes of cognitive sciences to offer a broader definition of presence, not related to technology only. Specifically, presence is described here as a core neuropsychological phenomenon whose goal is to produce a sense of agency and control: subjects are “present” if they are able to enact in an external world their intentions. This framework suggests that any environment, virtual or real, does not provide undifferentiated information, ready-made objects equal for everyone. It offers different opportunities and produces presence according to its ability in supporting the users and their intentions. The possible consequences of this approach for the development of presence-inducing virtual environments are also discussed.     

Stereoselective Biocatalyzed Reductions of Ginger Active Components Recovered from Industrial Wastes

Ginger is among the most widespread and widely consumed traditional medicinal plants around the world. Its beneficial effects, which comprise e. g. anticancer and anti-inflammatory activities as well as gastrointestinal regulatory effects, are generally attributed to a family of non-volatile compounds characterized by an arylalkyl long-chained alcohol, diol, or ketone moiety. In this work, ginger active components have been successfully recovered from industrial waste biomass of fermented ginger. Moreover, their recovery has been combined with the first systematic study of the stereoselective reduction of gingerol-like compounds by isolated alcohol dehydrogenases (ADHs), obtaining the enantioenriched sec-alcohol derivatives via a sustainable biocatalytic path in up to >99 % conversions and >99 % enantiomeric/diastereomeric excesses.     

Characterization of pulp calcifications and changes in their composition after treatments with citric acid and ethylenediaminetetraacetic acid solutions

The ectopic calcifications of non-mineralized tissues can occur in several forms throughout life, such as pulpal calcification. The presence of pulp stones is a challenge in endodontic treatment because they partially or fully obliterate the pulp chamber hindering access to root canals and their subsequent shaping. This study aimed to determine their crystallographic properties and evaluate the capacity of citric acid (CA) and ethylenediaminetetraacetic acid (EDTA) to promote the demineralization of pulp calcifications. The samples were obtained from patients with indications of endodontic treatment, and the radiographic examination was suggestive of pulp stone in at least one permanent tooth. The samples were isolated and analyzed by scanning electron microscopy/energy-dispersive x-ray spectroscopy (SEM/EDX). The Fourier Transform by high resolution-transmission electron microscopy, Raman microscopy, and X-ray diffraction (XRD) were used to identify the mineral phase and crystallographic characteristics. To evaluate the effect of CA and EDTA on the crystallinity of calcifications, they were submerged into these two individual solutions and the changes were assessed in situ by Raman spectroscopy. The SEM images obtained from calcifications demonstrated irregular morphologies. EDX of sample surfaces shows a high presence of oxygen, carbon, calcium, and phosphorous, however, other elements such as sodium, magnesium, nitrogen, chlorine, potassium, sulfur, and zinc were identified in less quantity. According to Raman, XRD, and high-resolution transmission electron microscopy, the predominant mineral phase identified in the pulpal calcification was a poor crystallinity apatite. According to in situ analyses, the effect of CA and EDTA was observed on the signals of PO₄³⁻ and CH₂ groups corresponding to inorganic and organic components. The changes with CA were evident at 7 min while the effect of EDTA was observed until 15 min of treatment. All results indicate that pulp stones have a heterogeneous composition principally composed of apatite with low crystallinity. The solubility of these pathological minerals is adequate using solutions such as EDTA or CA; however, the effectivity depends on the mineralization grade of calcifications, time, and concentration of exposition to this chemical.