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Abstract: Titanium reduced oxides TiO2–x occupy, since long time, a prominent place on the landscape of binary metal oxides because of their intriguing ability to form extended defects that affect both the formation of new superlattices and different electronic behaviours. Related to these features, a wide range of practical applications has been achieved. Moved by the conviction of the great potential of understanding the influence of the reactivity, compositional variations and size effects on their functional properties, the aim of this personal account is the optimization of a recently developed strategy for the stabilization of low n TinO2n–1 terms. In particular, we will focus on the Ti4O7 composition as well as the incorporation of transition metals, like Mn, in order to deal with new reduced Magnéli phases. [ABSTRACT FROM AUTHOR]

Consumption of wild mushrooms has increased in recent years; however, not all of them are edible and there is no precise information on those that may cause poisoning. Therefore, studies to obtain data about their toxicity are needed. For this purpose, we used the brine shrimp Artemia franciscana, a crustacean employed in toxicity tests and with wide application in the toxin detection, including mycotoxins. Mushrooms were collected in the state of Jalisco, Mexico, with which aqueous extracts were prepared. Dilutions of the stock solution of each extract were made to final concentrations of 50, 100, 250, 500, and 1000 µg/mL. Potassium dichromate (PD) was used as positive control and artificial seawater as negative control. The median lethal dose (LD50) of extracts on nauplii of A. franciscana was calculated. The aqueous extracts obtained from Amanita amerivirosa, A. muscaria, Chlorophyllum molybdites, and Leucopaxillus amarus showed a LD50 < 70 µg/mL, similar to PD (LD50 = 37 µg/mL). This is the first indication of the probable toxicity of Leucopaxillus amarus in humans. Cantharellus cibarius and Scleroderma texense caused the lower toxicity to the nauplii. The brine shrimp bioassay was effective in evaluating the toxicity of Basidiomycota. Scleroderma texense has been reported to be toxic, but it was not for this crustacean nauplii, and probably not to humans either, as recent literature has reported.

Mechanically interlocked derivatives of carbon nanotubes (MINTs) are interesting nanotube products since they show high stability without altering the carbon nanotube structure. So far, MINTs have been synthesized using ring-closing metathesis, disulfide exchange reaction, H-bonding or direct threading with macrocycles. Here, we describe the encapsulation of single-walled carbon nanotubes within a palladium-based metallosquare. The formation of MINTs was confirmed by a variety of techniques, including high-resolution transmission electron microscopy. We find the making of these MINTs is remarkably sensitive to structural variations of the metallo-assemblies. When a metallosquare with a cavity of appropriate shape and size is used, the formation of the MINT proceeds successfully by both templated clipping and direct threading. Our studies also show indications on how supramolecular coordination complexes can help expand the potential applications of MINTs., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The building of van der Waals heterostructures and the decoration of 2D materials with organic molecules share a common goal: to obtain ultrathin materials with tailored properties. Performing controlled chemistry on van der Waals heterostructures would add an extra level of complexity, providing a pathway towards 2D-2D-0D mixed-dimensional heterostructures. Here we show that thiol-ene-like "click" chemistry can be used to decorate franckeite, a naturally occurring van der Waals heterostructure with maleimide reagents. ATR-IR and NMR analyses corroborate the Michael addition mechanism via the formation of a S-C covalent bond, while Raman and HR-TEM show that the SnS2-PbS alternating structure of franckeite is preserved, and suggest that SnS2 reacts preferentially, which is confirmed through XPS. We illustrate how this methodology can be used to add functional molecular moieties by decorating franckeite with porphyrins. UV-vis-NIR spectroscopy confirms that the chromophore ground state remains operative, showing negligible ground-state interactions with the franckeite. Excited-state interactions across the hybrid interface are revealed. Time-resolved photoluminescence confirms the presence of excited-state deactivation in the linked porphyrin ascribed to energy transfer to the franckeite.

We describe the synthesis of rotaxane-type species composed of macrocyclic porphyrin rings mechanically interlocked with SWCNT threads. The formation of mechanically interlocked SWCNTs (MINTs) proceeds with chiral selectivity, and was confirmed by spectroscopic and analytical techniques and adequate control experiments, and corroborated by high-resolution electron microscopy. From a thorough characterization of the MINTs through UV-vis-NIR absorption, fluorescence, Raman, and transient absorption spectroscopy we analyse in detail the electronic interactions of the porphyrins and the SWCNTs in the ground and excited states.

Due to their outstanding electronic and mechanical properties, single-walled carbon nanotubes (SWCNTs) are promising nanomaterials for the future generation of optoelectronic devices and composites. However, their scarce solubility limits their application in many technologies that demand solution-processing of high-purity SWCNT samples. Although some non-covalent functionalization approaches have demonstrated their utility in extracting SWCNTs into different media, many of them produce short-lived dispersions or ultimately suffer from contamination by the dispersing agent. Here, we introduce an unprecedented strategy that relies on a cooperative clamping process. When mixing (6,5)SWCNTs with a dinucleoside monomer that is able to self-assemble in nanorings via Watson-Crick base-pairing, a synergistic relationship is established. On one hand, the H-bonded rings are able to associate intimately with SWCNTs by embracing the tube sidewalls, which allows for an efficient SWCNT debundling and for the production of long-lasting SWCNT dispersions of high optical quality along a broad concentration range. On the other, nanoring stability is enhanced in the presence of SWCNTs, which are suitable guests for the ring cavity and contribute to the establishment of multiple cooperative noncovalent interactions. The inhibition of these reversible interactions, by just adding, for instance, a competing solvent for hydrogen-bonding, proved to be a simple and effective method to recover the pristine nanomaterial with no trace of the dispersing agent.

The encapsulation of viologen derivatives into metallic single-walled carbon nanotubes (SWNTs) results in the opening of a band gap, making the SWNTs semiconducting. Raman spectroscopy, thermogravimetric analysis, and aberration-corrected high-resolution transmission electron microscopy confirm the encapsulation process. Through the fabrication of field-effect transistor devices, the change of the electronic structure of the tubes from metallic to semiconducting upon the encapsulation is confirmed. The opening of a gap in the band structure of the tubes was not detected in supramolecular controls., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Extensive research has been devoted to the chemical manipulation of carbon nanotubes. The attachment of molecular fragments through covalent-bond formation produces kinetically stable products, but implies the saturation of some of the C-C double bonds of the nanotubes. Supramolecular modification maintains the structure of the SWNTs but yields labile species. Herein, we present a strategy for the synthesis of mechanically interlocked derivatives of SWNTs (MINTs). In the key rotaxane-forming step, we employed macrocycle precursors equipped with two π-extended tetrathiafulvalene SWNT recognition units and terminated with bisalkenes that were closed around the nanotubes through ring-closing metathesis (RCM). The mechanically interlocked nature of the derivatives was probed by analytical, spectroscopic, and microscopic techniques, as well as by appropriate control experiments. Individual macrocycles were observed by HR STEM to circumscribe the nanotubes., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The structural and magnetic properties of a collection of nanoparticles coated by Poly(methyl methacrylate) through a wet chemical synthesis have been investigated. The particles display either an amorphous (M = Fe, Co) M-B arrangement or a mixed structure bcc-Fe and fcc-Co + amorphous M-B. Both show the presence of a metal oxi-hydroxide formed in aqueous reduction. The organic coating facilitates technological handling. The cost-effective synthesis involves a reduction in a Poly(methyl methacrylate) aqueous solution of iron(II) or cobalt(II) sulphates (< 0.5 M) by sodium borohydride (< 0.5 M). The particles present an oxidized component, as deduced from X-ray diffraction, Mössbauer and Fe- and Co K-edge X-ray absorption spectroscopy and electron microscopy. For the ferrous alloys, this Fe-oxide is alpha-goethite, favoured by the aqueous solution. The Poly(methyl methacrylate) coating is confirmed by Fourier transform infrared spectroscopy. In pure amorphous core alloys there is a drastic change of the coercivity from bulk to around 30 Oe in the nanoparticles. The mixed structured alloys also lie in the soft magnetic regime. Magnetisation values at room temperature range around 100 emu/g. The coercivity stems from multidomain particles and their agglomeration, triggering the dipolar interactions.

Two complex perovskite-related structures were solved by ab initio from precession electron diffraction intensities. Structure models were firstly derived from HREM images and than have been confirmed independently using two and three-dimensional sets of precession intensities. Patterson techniques prove to be effective for ab initio structure resolution, specially in case of projections with no overlapping atoms. Quality of precession intensity data may be suitable enough to resolve unknown heavy oxide structures.

A new perovskite-related oxide with the LaBaCuCoO5.2 composition has been stabilised. Its structure can be described as formed by the recurrent intergrowth of two alternating blocks of YBaCuFeO5 (2ac, i.e., two-fold perovskite superlattice) and YBa2Fe3O8 (3ac) structural types. From the starting material LaBaCuCoO5.2-delta (delta = 0), the rigorous control of the oxygen content has allowed the stabilisation of three new five fold perovskite-related superstructures with the compositions delta = 0.4, 0.8 and 1.1, which can also be described as recurrent intergrowths of two blocks showing 2ac and 3ac periodicity. The reduction process takes place through the 3ac periodic blocks, when 0 < delta < 0.8. Further oxygen decrease seems to involve the 2ac periodic blocks made up of pyramidal layers, giving rise to infinite layer units. The stability limit for these fivefold superstructures is delta = 1.1. In agreement with this the as-synthesised materials constitute an example of topotactic reaction, since their basic structure is kept through the reduction process.

Objective: To determine incidence, etiologic agents and clinical manifestations of bacterial meningitis in patients hospitalized in the newborn ward at the Hospital Infantil de Mexico in Mexico City and establish the incidence of meningitis in newborns admitted with respiratory distress syndrome (RDS) and determine how often blood cultures are negative in bacterial meningitis in this population., Methods: Retrospective chart review of patients with bacterial meningitis admitted to our hospital., Study Period: January 1990-July 1995., Results: There were 959 admissions to the neonatal intensive care unit (NICU). The overall incidence of bacterial meningitis was 32.3/1000 admissions; however, among 170 patients with RDS, [corrected] meningitis was detected in one (5.9/1000 RDS patients). Of the 31 patients with bacterial meningitis, 10 were preterm (PT) and 21 term (T). In the cerebrospinal fluid (CSF) isolates, there was a predominance of gram negative rods (n: 19; 61%). Clinical findings associated to meningitis were non-specific and there were no differences between PT and T infants. From 31 patients, 19 had negative blood cultures at the time of diagnosis (61%). Mortality associated to bacterial meningitis was [corrected] 40% and 23%, for PT and T, respectively (p = NS)., Conclusions: The incidence of bacterial meningitis in the study population was high. Most isolates in CSF were gram-negative rods. Clinical findings in meningitis were non-specific and there were no differences between PT and T. Most of the patients (61%) had negative blood cultures at the time of diagnosis.

An analytic relationship between positivity of the indirect immunofluorescent test (IIFT) for toxoplasmosis and clinical findings in a population of 328 children with cerebral infantile palsy (CIP) was performed. Children were distributed by age in one of four groups: I (0-2 years); II (3-6 years); III (7-12 years) and IV (13-18 years). One control group of 168 children with no PCI clinical findings was included. 125 sera were positive at 1:64 dilutions. The study of the binomial mother-child of 40 cases rendered 26 mothers with significant titer values. The majority of positive mothers to IIFT correlated with the youngest children (Groups I, II and III), mainly with group I (70.0%), which showed the highest titer ranges. Correlation between positive IIFT and clinical features was as high as 100.0%.

Toxocariosis is a zoonosis which has been widely studied in dogs. However, not much is known about this parasitosis in cats. The aim of the present work was to determine the frequency of Toxocara cati in domestic cats in Mexico City and the State of Mexico. Feces of 660 domestic cats were studied by the Faust concentration-floating test; 401 samples were from cats living in Mexico City of which 308 lived in houses and 93 in apartments; 231 were from urban areas of the State of Mexico and 28 from a rural area of the same state. The total frequency of T. cati eggs obtained from domestic cats in Mexico City was 42.9%; in cats living in apartments it was 18.3% and in cats living in houses it was 50.3%. In domestic cats from the State of Mexico, T. cati frequency was 36.4% in the urban and 21.4% in the rural areas. We consider that toxocariosis frequency observed at the two studied sites is high and that the need to prevent dissemination of the infectious forms of T. cati is urgent, as is the necessity of informing the population of the risk of living with T. cati parasited animals and of the anatomopathological alterations caused by T. cati in man.