Air-Stable Cobalt(III) and Chromium(III) Complexes as Single-Component Catalysts for the Activation of Carbon Dioxide and Epoxides.

Cobalt(III) and chromium(III) salophen chloride complexes were synthesized and tested for the cycloaddition of carbon dioxide (CO2) with epoxides to obtain cyclic carbonates. The cat1, cat2, cat4, and cat5 complexes presented high catalytic activity without cocatalysts and are solvent-free at 100 °C, 8 bar, and 9 h. At these conditions, the terminal epoxides (1a-1k) were successfully converted into the corresponding cyclic carbonates with a maximum conversion of ∼99%. Moreover, cat5 was highlighted due to its capability of opening internal epoxides such as limonene oxide (1l) with a 36% conversion to limonene carbonate (2l), and from cyclohexene oxide (1m), cyclic trans-cyclohexene carbonate (2m) and poly(cyclohexene carbonate) were obtained with 15% and 85% selectivity, respectively. A study of the coupling reaction mechanism was proposed with the aid of electrospray ionization mass spectrometry (ESI-MS) analysis, confirming the single-component behavior of the complexes through their ionization due to epoxide coordination. In addition, crystallographic analysis of cat1 single crystals grown in a saturated solution of pyridine helped to demonstrate that the substitution of chloride ion by pyridine ligands to form an octahedral coordination occurs (Py-cat1), supporting the proposed mechanism. Also, a recyclability study was performed for cat5, and a total turnover number of 952 was obtained with only minor losses in catalytic activity after five cycles.

(Dimethylamino)methylene hydantoins as building blocks in the synthesis of oxoaplysinopsins and parabanic acids with antifungal activity.

A short, efficient, and stereoselective methodology is described for the synthesis of 5-((dimethylamino)methylene)hydantoins and their conversion into oxoaplysinopsins and parabanic acids. A highly convergent one-pot, two-step reaction between methyl N-arylglycinates, isocyanates, and DMFDMA under microwave irradiation provided the corresponding (dimethylamino)methylene hydantoins as a single E-stereoisomer in high overall yields. The synthesis of (S)-1-(1-phenylethyl) chiral hydantoins, which undergo a stereoselective addition of acetic anhydride, aza-heterocycles, and amines, received special attention. The reaction with indole delivered a series of novel oxoaplysinopsins. Meanwhile, parabanic acids were prepared by a new approach, treating (dimethylamino)methylene hydantoins with mCPBA to generate the oxidative fragmentation of the exocyclic methylene. The antifungal evaluation of the prepared products was carried out on a series of Candida spp., finding potent growth inhibition. According to previous docking studies, this activity is probably due to the inhibitory interaction of the derivatives with the active site of the fungal HMGR enzyme.

Mercury in aquatic ecosystems of two indigenous communities in the Piedmont Ecuadorian Amazon: evidence from fish, water, and sediments.

Mercury is a highly toxic element present in water, soil, air, and biota. Anthropogenic activities, such as burning fossil fuels, mining, and deforestation, contribute to the presence and mobilization of mercury between environmental compartments. Although current research on mercury pathways has advanced our understanding of the risks associated with human exposure, limited information exists for remote areas with high diversity of fauna, flora, and indigenous communities. This study aims to deepen our understanding of the presence of total mercury in water, sediments, and fish, within aquatic ecosystems of two indigenous territories: Gomataon (Waorani Nationality) and Sinangoé (Ai´Cofán Nationality) in the Ecuadorian Amazon. Our findings indicate that, for most fish (91.5%), sediment (100%) and water (95.3%) samples, mercury levels fall under international limits. For fish, no significant differences in mercury levels were detected between the two communities. However, eight species exceeded recommended global limits, and one surpassed the threshold according to Ecuadorian legislation. Piscivore and omnivore fish exhibited the highest concentrations of total mercury among trophic guilds. Only one water sample from each community's territory exceeded these limits. Total mercury in sediments exhibited greater concentrations in Gomataon than Sinangoé. Greater levels of mercury in sediments were associated with the occurrence of total organic carbon. Considering that members of the communities consume the analyzed fish, an interdisciplinary approach, including isotopic analysis, methylmercury sampling in humans, and mercury monitoring over time, is imperative for a detailed risk assessment of mercury exposure in Amazonian communities.

The impact of COVID-19 on the peer relationships of adolescents around the world: A rapid systematic review.

The main objective of this rapid systematic review was to examine how the COVID-19 pandemic impacted peer relationships for adolescents (10-25 years of age) around the globe. We focused on four indices of peer relationships: (1) loneliness, (2) social connectedness, (3) social support, and (4) social media use. In addition, we examined gender and age differences. Four databases (APA PsychInfo, PubMed, Scopus, and Web of Science) were searched for articles published from January 2020 to November 2022. A total of 96 studies (cross-sectional: n = 66, longitudinal: n = 30, quantitative: n = 67, qualitative: n = 12, mixed-methods: n = 17) met our inclusion criteria (empirical observational studies with data on at least one of the indices of interest, cross-sectional data on COVID-19-related experiences or longitudinal data collected during the pandemic, age range of 10-25 years, typically developing adolescents). We extracted data and conducted a narrative synthesis. Findings suggest that COVID-19 disruptions negatively impacted peer relationships for youth. Most studies reported either an increase in loneliness over the course of the pandemic or a positive association between loneliness and COVID-19-related experiences. Similar findings were observed for increased social media use as a means of continued communication and connection. Fewer studies focused on social support but those that did reported a decrease or negative association with COVID-19-related experiences. Lastly, findings suggest a mixed impact on social connectedness, which might be due to the strengthening of closer ties and weakening of more distant relationships. Results for gender differences were mixed, and a systematic comparison of differences across ages was not possible. The heterogeneity in measures of COVID-19-related experiences as well as timing of data collection prevented a more nuanced examination of short and more long-term impacts.

Biological Activity of Complexes Involving Nitro-Containing Ligands and Crystallographic-Theoretical Description of 3,5-DNB Complexes.

Drug resistance in infectious diseases developed by bacteria and fungi is an important issue since it is necessary to further develop novel compounds with biological activity that counteract this problem. In addition, new pharmaceutical compounds with lower secondary effects to treat cancer are needed. Coordination compounds appear to be accessible and promising alternatives aiming to overcome these problems. In this review, we summarize the recent literature on coordination compounds based on nitrobenzoic acid (NBA) as a ligand, its derivatives, and other nitro-containing ligands, which are widely employed owing to their versatility. Additionally, an analysis of crystallographic data is presented, unraveling the coordination preferences and the most effective crystallization methods to grow crystals of good quality. This underscores the significance of elucidating crystalline structures and utilizing computational calculations to deepen the comprehension of the electronic properties of coordination complexes.

Measurements of Arterial Occlusion Pressure Using Hand-Held Devices.

ABSTRACT: Vehrs, PR, Reynolds, S, Allen, J, Barrett, R, Blazzard, C, Burbank, T, Hart, H, Kasper, N, Lacey, R, Lopez, D, and Fellingham, GW. Measurements of arterial occlusion pressure using hand-held devices. J Strength Cond Res 38(5): 873-880, 2024-Arterial occlusion pressure (AOP) of the brachial artery was measured simultaneously using Doppler ultrasound (US), a hand-held Doppler (HHDOP), and a pulse oximeter (PO) in the dominant (DOM) and nondominant (NDOM) arms of males ( n = 21) and females ( n = 23) using continuous (CONT) and incremental (INCR) cuff inflation protocols. A mixed-model analysis of variance revealed significant ( p < 0.05) overall main effects between AOP measured using a CONT (115.7 ± 10.9) or INCR (115.0 ± 11.5) cuff inflation protocol; between AOP measured using US (116.3 ± 11.2), HHDOP (115.4 ± 11.2), and PO (114.4 ± 11.2); and between males (120.7 ± 10.6) and females (110.5 ± 9.4). The small overall difference (1.81 ± 3.3) between US and PO measures of AOP was significant ( p < 0.05), but the differences between US and HHDOP and between HHDOP and PO measures of AOP were not significant. There were no overall differences in AOP between the DOM and NDOM arms. Trial-to-trial variance in US measurements of AOP was not significant when using either cuff inflation protocol but was significant when using HHDOP and PO and a CONT cuff inflation protocol. Bland-Altman plots revealed reasonable limits of agreement for both HHDOP and PO measures of AOP. The small differences in US, HHDOP, and PO measurements of AOP when using CONT or INCR cuff inflation protocols are of minimal practical importance. The choice of cuff inflation protocol is one of personal preference. Hand-held Doppler of PO can be used to assess AOP before using blood flow restriction during exercise.

Sequence analysis of SWEET transporters from trypanosomatids and evaluation of its expression in Trypanosoma cruzi.

Trypanosoma cruzi is an obligate parasite that uses glucose as one of the main resources to maintain its survival and proliferation. In eukaryotic cells glucose transport across membranes is mediated by facilitated transport through a variety of transporters. Herein, genes from the recently described SWEET family of carbohydrate transporters were identified in trypanosomatid parasites, including the medically important species T. cruzi and Leishmania spp. The identified genes have sequences with the typical attributes of known SWEET transporters. The expression of TcSWEET, the gene for the SWEET transporter found in the T. cruzi genome, was evidenced by immunohistochemistry using a polyclonal serum raised against peptides selected from the deduced TcSWEET protein sequence. In Western blot analysis, this α-TcSWEET serum detected proteins within the theoretical molecular mass for TcSWEET (25.8 kDa) in total epimastigote lysates, suggesting its expression at this parasite stage. Additionally, this serum stained epimastigotes at localizations consistent with the cell body and the flagellum. Together, these data suggests that SWEET transporters may contribute to glucose transport in trypanosomatid parasites.

Análisis de la presencia de trisomía 8 en las diferentes fases de leucemia mieloide crónica.

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Short Research Article: Promoting digital citizenship through a school-based intervention in early adolescence in Perú (a pilot quasi-experimental study).

OBJECTIVE: Evaluate the preliminary effectiveness of a school-based intervention to promote digital citizenship (DC) in Perú. METHODS: We piloted a translation and cultural adaptation of a DC curriculum originally designed for the U.S. with students in Perú. Students were assigned to either the Intervention group (n = 136, 52% female; mean age = 13.3) or Control group (n = 130, 55% female; mean age = 13.4). Students in the Control group continued with "business-as-usual" during their advisory period while the Intervention group received the DC curriculum. RESULTS: We found limited evidence that the DC curriculum can promote positive online experience and online conflict resolution skills, as well as increase knowledge regarding DC terms and concepts. However, the lack of strong effects suggests the need to revise materials, improve implementation and consider further adaptations. Nonetheless, results from this proof-of-concept study provide building blocks for future implementations of DC interventions for youth in Latin America.

The origins of global biodiversity on land, sea and freshwater.

Many biodiversity studies focus on explaining high tropical species richness, but an equally dramatic yet understudied pattern involves the divergent richness of land, sea and freshwater. Here, we reveal the origins of these richness differences among habitats across animals and plants. Most plant and animal species are terrestrial, although these habitats cover only ~28% of Earth's surface. Marine habitats have fewer species over a larger area (~70%). Freshwater habitats have relatively high richness and exceptional phylogenetic diversity given their tiny area (2%). The relative richness of habitats is related to variation in diversification rates. Based on ancestral reconstructions of habitat, we find that most marine species are descended from marine ancestors and most terrestrial species from freshwater ancestors. Yet, most extant animal richness in freshwater is derived from terrestrial ancestors. Overall, our results reveal the origins of fundamental but neglected biodiversity patterns, and highlight the conservation importance of freshwater habitats.

Pregnant Latinas' views of adopting exome sequencing into newborn screening: A qualitative study.

PURPOSE: There are, currently, conflicting opinions about the adoption of exome sequencing (ES) into the standard newborn screening program. This study aimed to explore the views of pregnant Latinas, a hard-to-reach, underserved, and understudied population, about pursuing ES for their newborns. METHODS: We conducted semistructured interviews with 32 pregnant Latinas who predominately lived in rural areas and had low levels of income and education. An emergent coding approach was used to analyze the qualitative data collected. RESULTS: Our entire sample believed that ES should be offered as a part of newborn screening, which could empower pregnant Latinas to better understand their children's health and take early treatment actions. Although some participants were concerned about potentially bad ES results and had questions about the accuracy of ES results, nearly all interviewees reported that they would be willing to have their newborns undergo ES. The main reasons given were to be informed of diseases that the baby may have, and the perception that ES is a procedure that involves minimal risk. CONCLUSION: Pregnant Latinas in this study had favorable attitudes toward newborn ES. Their perspectives should be considered when decisions are made about incorporating ES into newborn screening.

Real-Time Analysis of Polyphenol-Protein Interactions by Surface Plasmon Resonance Using Surface-Bound Polyphenols.

A selection of bioactive polyphenols of different structural classes, such as the ellagitannins vescalagin and vescalin, the flavanoids catechin, epicatechin, epigallocatechin gallate (EGCG), and procyanidin B2, and the stilbenoids resveratrol and piceatannol, were chemically modified to bear a biotin unit for enabling their immobilization on streptavidin-coated sensor chips. These sensor chips were used to evaluate in real time by surface plasmon resonance (SPR) the interactions of three different surface-bound polyphenolic ligands per sensor chip with various protein analytes, including human DNA topoisomerase IIα, flavonoid leucoanthocyanidin dioxygenase, B-cell lymphoma 2 apoptosis regulator protein, and bovine serum albumin. The types and levels of SPR responses unveiled major differences in the association, or lack thereof, and dissociation between a given protein analyte and different polyphenolic ligands. Thus, this multi-analysis SPR technique is a valuable methodology to rapidly screen and qualitatively compare various polyphenol-protein interactions.

Differential tissue distribution of discrete typing units after drug combination therapy in experimental Trypanosoma cruzi mixed infection.

The aim of the present work was to evaluate the distribution of the different clones of the parasite prevailing after treatment with benznidazole (BZ) and clomipramine (CLO), in mice infected with Trypanosoma cruzi, Casibla isolate which consists of a mixture of two discrete typing units (DTUs). Albino Swiss mice were infected and treated with high and low concentrations of BZ (100 or 6.25 mg/kg), CLO (5 or 1.25 mg/kg), or the combination of both low doses (BZ6.25 + CLO1.25), during the acute phase of experimental infection. Treatment efficacy was evaluated by comparing parasitaemia, survival and tissular parasite presence. For DTUs genotyping, blood, skeletal and cardiac muscle samples were analysed by multiplex quantitative polymerase chain reaction. The combined treatment had similar outcomes to BZ6.25; BZ100 was the most effective treatment, but it failed to reach parasite clearance and produced greater histological alterations. Non-treated mice and the ones treated with monotherapies showed both DTUs while BZ6.25 + CLO1.25 treated mice showed only TcVI parasites in all the tissues studied. These findings suggest that the treatment may modify the distribution of infecting DTUs in host tissues. Coinfection with T. cruzi clones belonging to different DTUs reveals a complex scenario for the treatment of Chagas disease and search for new therapies.

A Mixed-Methods Study Examining Adherence to and Acceptability of Intravaginal Rings for HIV Prevention: Behavioral Results of MTN-027.

Intravaginal rings (IVR) containing antiretroviral drugs are a promising method for HIV prevention. We triangulated quantitative and qualitative assessments to evaluate the acceptability of four IVRs used continuously for 28 days as part of a Phase I trial (N = 48 HIV-negative women; ages 18-45). Adherence was high throughout the trial, yet 30% of participants reported involuntary IVR expulsions followed by re-insertion. Most participants (93.6%) felt comfortable with the IVR being inside their body. Participants reported liking the IVR more (36.2%) or the same amount (55.3%) since starting the study. When given the option of choosing between the IVR and/or a male condom for HIV-prevention, most reported preferring the IVR (n = 29, 63.0%), and over a quarter of the sample reported liking them equally (n = 12, 26.1%). We observed no differences in IVR acceptability across the study arms. High adherence and acceptability underscores the promise of an IVR as a female-controlled, sustained mechanism for HIV prevention.

[Validation of the Ocular Surface Disease Index Questionnaire for Chilean patients]. / Adaptación cultural y validación del cuestionario Ocular Surface Disease Index en una población chilena.

BACKGROUND: Ocular Surface Disease Index (OSDI) is the most commonly used questionnaire worldwide to detect dry eye disease. Although it is massively used in clinical practice in Chile, its use has not been validated yet in the country. AIM: To develop a cultural adaptation and to validate the OSDI questionnaire for the Chilean population. MATERIAL AND METHODS: For cultural adaptation, a translation, retro-translation and an expert panel review was carried out. The resulting questionnaire was applied to a pilot group of twelve participants and their comments were considered for the final questionnaire version. The final questionnaire was applied to a non-random sample of 200 patients aged 53 ± 17 years (75% women). Internal consistency and construct validity were evaluated by Cronbach's alpha and exploratory factor analysis respectively. RESULTS: According to the OSDI score, 81% of respondents had dry eye (55% severe). Reliability was 0.91 and factor analysis resulted in three factors explaining 75.4% of the total variance. CONCLUSIONS: The OSDI questionnaire version obtained in this study demonstrated excellent internal consistency values and adequate construct validity making it applicable to clinical practice and dry eye research.

Possible female philopatry of the smooth hammerhead shark Sphyrna zygaena revealed by genetic structure patterns.

We assessed the spatial pattern of genetic structure of smooth hammerhead shark Sphyrna zygaena in 10 localities from the Northern Mexican Pacific. A total of 35 haplotypes were identified in 129 sequences of the mtDNA control region. The results showed slight but significant genetic structure among localities (ΦST = 0.044, P < 0.001). In addition, the localities with highest number of juveniles were genetically different (ΦST = 0.058, P < 0.024), which may be representative of nursery areas. The genetic differentiation pattern can be associated to female philopatry and preference for particular birthing sites. Finally, historical demography shows that S. zygaena populations present a recent demographic expansion that occurred during glacial events in the late Pleistocene to early Holocene.

Evaluation of phytotoxicity of effluents from activated sludge and constructed wetland system for wastewater reuse.

The aim of this study was to evaluate the phytotoxicity of wastewater treated with horizontal subsurface flow (HSSF) constructed wetlands (CWs) and activated sludge (AS) system using disinfection treatment such chlorination and ultraviolet (UV) system. To assess the impact of the reuse of different effluents (HSSF-Cl, HSSF-UV, AS-Cl and AS-UV), bioassays using seeds of Raphanus sativus (R. sativus) and Triticum aestivum (T. aestivum), were performed on both Petri dishes and soil. Different treated wastewater concentrations were varied (6.25%, 12.5%, 25%, 50% and 100%) and the percentage of germination inhibition (PGI), percentage of epicotyl elongation (PEE) and germination index (GI) were determined. Positive effects (PGI and PEE <0% and GI >80%) of HSSF-Cl, HSSF-UV, AS-Cl and AS-UV effluents on germination and epicotyl elongation of R. sativus and T. aestivum were observed in Petri dishes bioassays. However, toxic effects of HSSF-Cl, HSSF-UV and AS-Cl on seeds germination and epicotyl elongation of both plant species were detected in soil samples (PGI and PEE >0% and GI <80%). Only R. sativus seeds to be irrigated with AS-UV achieved GI values above 86% for all concentrations evaluated. These results indicated that AS-UV effluent had a positive effect on seeds germination and can be recommended for treated wastewater reuse in agricultural irrigation.

Volatiles and Nonvolatiles in Flourensia campestris Griseb. (Asteraceae), How Much Do Capitate Glandular Trichomes Matter?

The distribution and ultrastructure of capitate glandular trichomes (GTs) in Flourensia species (Asteraceae) have been recently elucidated, but their metabolic activity and potential biological function remain unexplored. Selective nonvolatile metabolites from isolated GTs were strikingly similar to those found on leaf surfaces. The phytotoxic allelochemical sesquiterpene (-)-hamanasic acid A ((-)-HAA) was the major constituent (ca. 40%) in GTs. Although GTs are quaternary ammonium compounds (QACs)-accumulating species, glycine betaine was not found in GTs; it was only present in the leaf mesophyll. Two (-)-HAA accompanying surface secreted products: compounds 4-hydroxyacetophenone (piceol; 1) and 2-hydroxy-5-methoxyacetophenone (2), which were isolated and fully characterized (GC/MS, NMR), were present in the volatiles found in GTs. The essential oils of fresh leaves revealed ca. 33% monoterpenes, 26% hydrocarbon- and 30% oxygenated sesquiterpenes, most of them related to cadinene and bisabolene derivatives. Present results suggest a main role of GTs in determining the volatile and nonvolatile composition of F. campestris leaves. Based on the known activities of the compounds identified, it can be suggested that GTs in F. campestris would play key ecological functions in plant-pathogen and plant-plant interactions. In addition, the strikingly high contribution of compounds derived from cadinene and bisabolene pathways, highlights the potential of this species as a source of high-valued bioproducts.

Progress in tear microdesiccate analysis by combining various transmitted-light microscope techniques.

BACKGROUND: Tear desiccation on a glass surface followed by transmitted-light microscopy has served as diagnostic test for dry eye. Four distinctive morphological domains (zones I, II, III and transition band) have been recently recognized in tear microdesiccates. Physicochemical dissimilarities among those domains hamper comprehensive microscopic examination of tear microdesiccates. Optimal observation conditions of entire tear microdesiccates are now investigated. One-µl aliquots of tear collected from individual healthy eyes were dried at ambient conditions on microscope slides. Tear microdesiccates were examined by combining low-magnification objective lenses with transmitted-light microscopy (brightfield, phase contrasts Ph1,2,3 and darkfield). RESULTS: Fern-like structures (zones II and III) were visible with all illumination methods excepting brightfield. Zone I was the microdesiccate domain displaying the most noticeable illumination-dependent variations, namely transparent band delimited by an outer rim (Ph1, Ph2), homogeneous compactly built structure (brightfield) or invisible domain (darkfield, Ph3). Intermediate positions of the condenser (BF/Ph1, Ph1/Ph2) showed a structured roughly cylindrical zone I. The transition band also varied from invisibility (brightfield) to a well-defined domain comprising interwoven filamentous elements (phase contrasts, darkfield). CONCLUSIONS: Imaging of entire tear microdesiccates by transmitted-light microscopy depends upon illumination. A more comprehensive description of tear microdesiccates can be achieved by combining illumination methods.

Sublethal Effects of Chlorine-Free Kraft Mill Effluents on Daphnia magna.

The implementation of elemental chlorine-free (ECF) bleaching methods has drastically reduced the aquatic toxicity of Kraft mill effluents during the last decade. However, the residual toxicity of Kraft mill effluents is still a potential concern for the environment, even when subjected to secondary wastewater treatment. The aim of this study is characterize potential sublethal effects of ECF Kraft mill effluents using Daphnia magna as model species. D. magna exposed towards increasing concentration of ECF Kraft mill effluent showed a significant, dose-dependent reduction in feeding. Conversely, post-feeding assay, life history, and allometric growth analyses showed stimulatory, rather than inhibitory effects in exposed animals at low concentrations, while high concentrations of ECF Kraft mill effluents reduced their reproductive output. These results suggest a hormetic effect in which moderate concentrations of the effluent had a stimulatory effect with higher concentrations causing inhibition in some variables.