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When (4n +2) π-electrons are located in single planar ring, it conventionally qualifies as aromatic. According Hückel's rule, systems possessing ten π-electrons should be aromatic. Herein we report a series of D 5h  Li 6 E 5 Li 6 sandwich structures, representing the first global minima featuring ten π-electrons E 5 10- ring (E=Si-Pb). However, these π-electrons localize as five π-lone-pairs rather than delocalized orbitals. The high symmetry structure achieved is a direct consequence of σ-aromaticity, particularly favored in elements from Si to Pb, resulting in a pronounced diatropic ring current flow that contributes to the enhanced stability of these systems., (© 2023 Wiley-VCH GmbH.)

Planar boron clusters have often been regarded as "π-analogous" to aromatic arenes because of their similar delocalized π-bonding. However, unlike arenes such as C 5 H 5 - and C 6 H 6 , boron clusters have not previously shown the ability to form sandwich complexes. In this study, we present the first sandwich complex involving beryllium and boron, B 7 Be 6 B 7 . The global minimum of this combination adopts a unique architecture having a D 6h geometry, featuring an unprecedented monocyclic Be 6 ring sandwiched between two quasi-planar B 7 motifs. The thermochemical and kinetic stability of B 7 Be 6 B 7 can be attributed to strong electrostatic and covalent interactions between the fragments. Chemical bonding analysis shows that B 7 Be 6 B 7 can be considered as a [B 7 ] 3- [Be 6 ] 6+ [B 7 ] 3- complex. Moreover, there is a significant electron delocalization within this cluster, supported by the local diatropic contributions of the B 7 and Be 6 fragments., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The synthesis of a series of 26-amino-22-oxocholestanes derived from diosgenin was accomplished via the substitution of an iodine atom at C-26 by primary and secondary amines. The reactions were conducted in refluxing acetonitrile and through microwave-assisted heating. The latter shows significant improvements in terms of reaction times going from hours to a few minutes or even seconds for completion. Only one of the selected amines, 4-aminourazole, did not yield the substitution product and the imine formation pathway was investigated instead, achieving the 26-iminourazole-22-oxocholestane. All the final products have been characterized and the cytotoxic activity of three of them has been evaluated in SiHa, MCF-7 and MDA tumor cell lines by the sulforhodamine B assay., (Copyright © 2022 Elsevier Inc. All rights reserved.)

22-Oxocholestanes bearing the oxime functionality in the side chain have been synthesized from diosgenin and evaluated in vivo as anti-inflammatory agents in an acute inflammation mouse ear model, against the commercial glucocorticoid dexamethasone. The final compounds were all regioselectively obtained with an E configuration at the oxime double bond. The title compounds reduced ear-induced inflammation and edema. The most active oximes repressed the expression of proinflammatory genes TNF-α, COX-2, and IL-6; including macrophage migration inhibitory factor. Overall, our data suggest that 22-oxocholestane oximes exert a strong in vivo anti-inflammatory activity., (Copyright © 2019 Elsevier Masson SAS. All rights reserved.)

We examined the sediments of four coastal lagoons (Ria Lagartos, Bocas de Dzilam, Laguna de Chelem and Ria Celestun) from the state of Yucatan, Mexico, for three widely used commercial polybrominated diphenyl ethers formulations (penta-, octa- and deca-BDE). The most commonly found congeners in all four lagoons were BDEs 47, 99 and 100 (all in the penta-BDE formulation) and BDE209 (deca-BDE formulation). The greatest variety and highest concentrations of brominated flame retardants were found in Ria Lagartos, which also showed the highest BDE 100 concentration (24.129 ng/g). Hexabromocyclododecane was found in all lagoons, but at lower concentrations than those of the various polybrominated diphenyl ethers. Dispersal routes of these compounds are discussed, such as a ring of sinkholes (cenotes) adjacent to the lagoons. Moreover, electronic waste is a serious problem because municipal landfills have been the primary disposal method for these wastes and therefore represent a reservoir of brominated fire retardants.

A comprehensive theoretical study of the oxygen reduction reaction (ORR) over B,N-codoped graphene has been carried out in the framework of DFT using two different approaches based on periodic or cluster models. The comparison and integration of the information provided by the two approaches allow achieving a more complete description of the studied phenomena, combining the advantages of both models. On one hand, the analysis of the structure, stability, and electronic properties of this catalyst permits to identify and characterize the active sites and provides insights into the origin of its high catalytic activity that should be found in the synergistic coupling of the opposite effects of the two B and N heteroatoms used as dopants. On the other hand, the study of the reaction mechanisms evidences that the process is thermodynamically favorable due to the overall high exothermicity, and that the 4e - transfer is the favorite ORR pathway, being the OH hydrogenation the rate-determining step. Overall, all the reported results clearly underline the superior catalytic activity of B,N-codoped graphene toward this reaction. © 2017 Wiley Periodicals, Inc., (© 2017 Wiley Periodicals, Inc.)

26-Hydroxycholestan-22-one derivatives with oxygenated functions in the rings A and/or B were successfully synthesized from diosgenin. After the modifications of rings A and B, the spiroketal side chain was selectively opened through a Lewis acid mediated acetolysis to afford the cholestane derivatives. These compounds incorporate pharmacophores, which mimic the activity of natural phytohormones and show high growth promoting activity in Mexican rice cultivars using the rice lamina inclination test., (Copyright © 2017 Elsevier Inc. All rights reserved.)

The spirostanic steroidal side-chain of diosgenin and hecogenin was modified to produce 22-oxocholestane derivatives. This type of side-chain was obtained in good yields through a straightforward four-step pathway. These compounds show potent brassinosteroid-like growth promoting activity evaluated via the rice lamina joint inclination bioassay. This is the first report of steroidal skeletons bearing the 22-oxocholestane side-chain and preserving the basic structure (A-D rings) from their corresponding parent compounds acting as plant growth promoters., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Reserve regulations at El Palmar State Reserve, Yucatan, Mexico, prohibit the use of lead (Pb) shot, but hunters continue to use it, and no enforcement is implemented. Pb was quantified in sediments and in blue-winged teal Anas discors. No shot pellets were found in the sediment samples, nor were differences in sediment Pb concentrations observed within the reserve between popular hunting sites and those no longer used for hunting. However, there were differences between the hunting sites and sediments from an adjacent area where hunting is prohibited. Average Pb concentrations were highest at hunting entrances (15.69 ± 18.69 mg/kg) and lowest at decoy locations (5.24 ± 4.84 mg/kg). These averages are lower than the lowest effects level (31 mg/kg), although 10 samples exceeded this level. Pb-shot prevalence in gizzards was 4.88% (n = 41). Pb levels exceeded 5.0 mg/kg dry weight in one or more of the tested tissues (liver, gizzard, and bone) in 14 (34.14%; 7 female, 7 male; 11 adult, 3 juvenile) of the total birds. Bird weight, sex, and age had no effect on Pb concentration. Hunting using Pb shot in the reserve clearly affects Pb levels in sediments and in A. discors that winter there.

Objective: To describe the safety of olanzapine treatment in adolescents (aged 13-17 years) with schizophrenia or bipolar I disorder, and to compare these data with those of olanzapine-treated adults., Data Sources and Study Selection: Placebo-controlled database, adolescents: acute phase of 2 double-blind, placebo-controlled trials (3-6 weeks; olanzapine, N = 179, mean age = 15.5 years; placebo, N = 89, mean age = 15.7 years); overall adolescent olanzapine exposure database, adolescents: 4 trials (e.g., the 2 aforementioned studies, each with a 26-week open-label extension phase, and 2 open-label, 4.5- and 24-week trials; N = 454, mean age = 15.9 years); and adult database: 84 clinical trials of up to 32 weeks., Data Synthesis: The mean daily dosage of olanzapine was 10.6 mg/day (exposure = 48,946 patient days). In the overall adolescent olanzapine exposure database, the most common adverse events included increased weight (31.7%), somnolence (19.8%), and increased appetite (17.4%). In up to 32 weeks of treatment, when compared with adults, adolescents from the overall adolescent olanzapine exposure database gained statistically significantly more weight (7.4 kg vs. 3.2 kg, p < .001); statistically significantly more adolescents gained > or = 7% of their baseline weight (65.1% vs. 35.6%, p < .001). Adolescents experienced statistically significant within-group baseline-to-endpoint changes in fasting glucose (p < .001), total cholesterol (p = .002), triglycerides (p = .007), and alanine aminotransferase (p < .001). Two patients from the overall adolescent olanzapine exposure database (0.4%) attempted suicide; 13 (2.9%) had suicidal ideation. In the placebo-controlled database, adolescents had statistically significant baseline-to-endpoint increases in prolactin (11.4 micrograms/L, p < .001); 47.4% had high prolactin levels., Conclusions: The types of adverse events in olanzapine-treated adolescents appear to be similar to those of adults. The magnitude and incidence of weight and prolactin changes were greater in adolescents., Trial Registration: clinicaltrials.gov Identifiers: NCT00051298, NCT00050206, and NCT00113594., (Copyright 2009 Physicians Postgraduate Press, Inc.)

The coastal environment of the Yucatan Peninsula (SE, Mexico) includes a wide variety of ecosystems ranging from mangroves to coral reefs, resulting in a heterogeneous landscape. Specifically, the marine system is characterized by environmental differences which respond to regional and local forcing functions such as marine currents and groundwater discharges (GD). Such functional characteristics were used here to define four subregions across the Yucatan coast and diagnose the health status of this coastal marine ecosystem. To achieve this goal, we conducted an analysis and integration of water quality variables, an eutrophic assessment, evaluated changes in submerged aquatic vegetation (SAV), and analyzed the community structure and distribution of harmful phytoplankton. The first step was to determine the reference values for each subregion based on data previously collected from 2002 to 2006 along the coast of Yucatan, 200m offshore. The trophic index (TRIX) and Canadian index for aquatic life (CCMEWQI) were used to diagnose each subregion and then the ASSETS approach was conducted for Dzilam and Progreso, sampling localities on each end of the health status continuum (those with the best and worst conditions). Overall, results indicated that the marine coastal ecosystem of Yucatan is in good condition; however, differences were observed between subregions that can be attributed to local forcing functions and human impacts. Specifically, the central region (zone HZII, Progreso-Telchac) showed symptoms of initial eutrophication due to nutrient inputs from human activities. The eastern region (zone HZ III, Dzilam-Las Bocas) showed a meso-eutrophic condition linked to natural groundwater discharges, while the other two subregions western (zone HZI Celestun-Palmar) and caribbean (zone HZ IV Ria Lagartos-El Cuyo) exhibited symptoms of oligo-mesotrophic condition. These findings may be considered baseline information for coastal ecosystem monitoring programs in Yucatan, and the approach used could be replicated for other coastal areas.

White grunt (Haemulon plumieri) has been proposed by the Mesoamerican Barrier Reef System (MBRS) Synoptic Monitoring Program as a bioindicator species. It is in this sense that the present study has a main goal to evaluate this organism's suitability as an indicator species. Individuals were captured during three seasons at the port of Sisal, Yucatan, Mexico which is located in an area that is considered to be weakly impacted by human activities such as agriculture or industry. Both cholinesterase (ChE) and carboxylesterase (CbE) activities were measured in brain, muscle, liver and eye of sampled individuals. Results indicated that ChE and CbE activities were greatest in the brain (256.3 ± 43) and in the liver (191 ± 21), respectively. Furthermore, ChEs detected in brain, liver and muscle were characterized, and results suggested that the acetylcholinesterase (AChE) type was more abundant relative to pseudocholinesterase (BChE) which was rare. In addition, K(m) and V(max) and IC(50) values were calculated from the Michaelis-Menten equation. Finally, an additional experiment in vitro showed a significant decrease in both ChE and CbE activities when different tissues were exposed to model xenobiotics, such as benzo[a]pyrene and Chlorpyrifos. In conclusion, findings from this study confirm the potential suitability of H. plumieri as an organic pollution bioindicator species, and thus of practical use for environmental biomonitoring purposes.

We studied whether polychlorinated biphenyls (PCBs) may alter the development of song control brain nuclei in zebra finch (Taeniopygia guttata) offspring of pulse-exposed hens. We orally administered 40 microg of Aroclor 1248 to adult female finches before egg laying. When the progeny were 50 d old, we measured the volumes of the song control nuclei robustus arcopallialis (RA) and higher vocal center (HVC) using light microscopy. Both male and female progeny of exposed birds had a significantly smaller RA than control birds (36 and 16%, respectively; p < or = 0.05). The HVC did not differ in either sex between exposed and control groups. Perhaps impaired development of RA was caused by PCB action on steroid receptors. We conclude that animals living in contaminated areas may be at risk of neurological damage in hormone-sensitive brain areas and that changes in brain nuclei related to song may be a sensitive indicator of low-level PCB exposure.

Several investigations have demonstrated that the increase in chemicals in the environment may have caused effects on aquatic life and wildlife. The impact from oil production activities on the benthic community structure and shrimp (Farfantepenaeus duorarum and Litopenaeus setiferus) biochemical markers were studied in the Gulf of Mexico, which is heavily contaminated by polycyclic aromatic hydrocarbons and heavy metals. Shrimp were collected from a control area and from an area close to oil production platforms during October and November 2002. There was no spatial difference in exposure and response probably because shrimp migrate, as results did not show significant differences in cytochrome P4501A (as measured by ethoxycoumarin O-deethylase (ECOD) metabolism) between the two sites. In October, shrimp ECOD activities were higher and statistically different from those measured in the samples taken in November. As for ECOD activities, with the concentration of vitellogenin as another biomarker, there were no differences between the shrimp collected from the control area and the shrimp collected on the oil production platforms. In this case the concentrations were higher in shrimp collected in November vs. shrimp collected in October. However, there are significant correlations between contaminants and responses (biomarkers), indicating an effect of pollution. One of the most important considerations brought up by this kind of study is that, although the majority of groups studying the effects of endocrine disruption have focused almost exclusively on human health or vertebrate wildlife-related issues, it is necessary to increase research focused on understanding the function of hormones in invertebrate species exposed in the field to different kinds of pollutants.