Mercury and selenium in biological pump under upwelling-downwelling influence in Cabo Frio shelf, South Atlantic Ocean, Brazil.

The knowledge of metals concentration in upwelling areas are a concern due the higher productivity of these areas In Cabo Frio Upwelling-Downwelling System (CFUS) is high primary productivity area and has been identified as an Hg hotspot to biota in SE Brazil that has been susceptible to Hg inputs, due to growing industrialization in the region. To investigate the concentration of Hg and Se metals, as well as the trophic transfer of these metals, the present study investigated Hg and Se concentrations in 64 samples collected in net mesh of >20, >64, >150 and >300 μm, in 2012, in the region's water masses. Higher mean Hg concentrations were found in zooplankton, 0.

Human-in-the-loop active learning for goal-oriented molecule generation.

Machine learning (ML) systems have enabled the modelling of quantitative structure-property relationships (QSPR) and structure-activity relationships (QSAR) using existing experimental data to predict target properties for new molecules. These property predictors hold significant potential in accelerating drug discovery by guiding generative artificial intelligence (AI) agents to explore desired chemical spaces. However, they often struggle to generalize due to the limited scope of the training data.

The Minnesota Critical Care Working Group 1: Monitoring and coordinating statewide critical care surge response in the COVID-19 pandemic, March 2020 through July 1, 2021.

Background: In response to the COVID-19 pandemic and as part of the statewide healthcare coalition response the Minnesota Critical Care Working Group (CCWG), composed of Interprofessional leaders from the state's nine largest health systems was established and entrusted to plan and coordinate critical care support for Minnesota from March 2020 through July1, 2021.

Research Question: Can a statewide Critical Care Working Group develop contingency and crisis level surge strategies and indicators in response to the COVID-19 pandemic while evolving into a highly collaborative team?

Study Design And Methods: CCWG members (Intensivists, ethicists, nurses, MDH and MHA leaders) met by audio video conferencing as often as daily assessing COVID and non-COVID hospitalization data, developed surge indicators reflecting contingency versus crisis conditions, and planned responses collaboratively. A foundation of collaboration and teamwork developed which facilitated an effective statewide response.

How can Community Music Help Address Loneliness in Contexts of Social Marginalisation? Insights From Two Music for Social Connection Programs.

This study explores how participatory music programs can help build social connection for people experiencing loneliness in contexts of social marginalisation. Loneliness is a growing, global public health issue with social and structural drivers. There is an urgent need to investigate innovative approaches to programming that go beyond opportunities for social contact to address the multiple domains of loneliness.

The Minnesota Critical Care Working Group 2: Crisis conditions during the COVID-19 Pandemic, July 2021 through March 2022.

Background: At the request of the Statewide Healthcare Coordination Center, the Minnesota Critical Care Working Group (CCWG) and ethics subgroup (EWG), composed of interprofessional leaders from Minnesota's nine largest health systems were asked to plan and coordinate critical care operations during the COVID-19 pandemic, including the 2021 Fall surge.

Research Question: Can a statewide Working Group collaboratively analyze real time evidence to identify crisis conditions and engage state leadership to implement care processes?

Study Design And Methods: CCWG/EWG met via video conferencing during the Fall 2021 severe surge to analyze evidence and plan for potential crisis care conditions. Five sources of evidence informed their actions including group consensus on operating conditions; Federal Tele-Tracking data; MOCC patient placement data; and two surveys created and distributed to hospitals and healthcare professionals.

The Glucose-Glutamine Metabolic Interplay in MCF-7 Cells, a Hormone-Sensitive Breast Cancer Model.

Background: Selective deprivation of glutamine has been shown to accelerate the generation of reactive oxygen species (ROS) and to impair the activity of a specific pentose phosphate pathway (PPP) located within the endoplasmic reticulum (ER). The consequent oxidative damage suggests that glucose flux through this reticular pathway might contribute to the redox stress of breast cancer cells. We thus evaluated whether this response is reproduced when the glutamine shortage is coupled with the glucose deprivation.

Exerting pulling forces in fluids by directional disassembly of microcrystalline fibres.

Biomolecular polymerization motors are biochemical systems that use supramolecular (de-)polymerization to convert chemical potential into useful mechanical work. With the intent to explore new chemomechanical transduction strategies, here we show a synthetic molecular system that can generate forces via the controlled disassembly of self-organized molecules in a crystal lattice, as they are freely suspended in a fluid. An amphiphilic monomer self-assembles into rigid, high-aspect-ratio microcrystalline fibres.

Free-Radical Deoxygenative Amination of Alcohols via Copper Metallaphotoredox Catalysis.

Alcohols are among the most abundant chemical feedstocks, yet they remain vastly underutilized as coupling partners in transition metal catalysis. Herein, we describe a copper metallaphotoredox manifold for the open shell deoxygenative coupling of alcohols with -nucleophiles to forge C()-N bonds, a linkage of high value in pharmaceutical agents that is challenging to access via conventional cross-coupling techniques. -heterocyclic carbene (NHC)-mediated conversion of alcohols into the corresponding alkyl radicals followed by copper-catalyzed C-N coupling renders this platform successful for a broad range of structurally unbiased alcohols and 18 classes of -nucleophiles.

Improving the Stability and Kinetic Inertness of Mn(II) Complexes by Increasing the Bridge Length in Bicyclic CDTA-Like Ligands.

Kinetic inertness of Mn(II)-based MRI contrast agents can be improved by increasing the rigidity of the polydentate ligand that tightly coordinate the metal ion. Taking inspiration from the remarkable increase in kinetic inertness of [Mn(CDTA)] compared to [Mn(EDTA)] due to the cyclohexyl backbone rigidity, we devised that bicyclic ligands would further improve the kinetic inertness of the Mn(II) complexes. The length of the alkyl bridge on the cyclohexane ring was varied from methylene (BCH-DTA), ethylene (BCO-DTA) to propylene (BCN-DTA) to evaluate the influence of the different trans-diaminotetraacetate ligands on relaxometric, thermodynamic and kinetic properties of the Mn(II) complexes.

The History of Flow Chemistry at Eli Lilly and Company.

Flow chemistry was initially used for speed to early phase material delivery in the development laboratories, scaling up chemical transformations that we would not or could not scale up batch for safety reasons. Some early examples included a Newman Kwart Rearrangement, Claisen rearrangement, hydroformylation, and thermal imidazole cyclization. Next, flow chemistry was used to enable safe scale up of hazardous chemistries to manufacturing plants.

Thermodynamic and Kinetic Stabilities of Al(III) Complexes with NO Pentadentate Ligands.

Al(III) complexes have been recently investigated for their potential use in imaging with positron emission tomography (PET) by formation of ternary complexes with the radioisotope fluorine-18 (F). Although the derivatives of 1,4,7-triazacyclononane-1,4,7-triacetic acid (NOTA) are the most applied chelators for [AlF] labelling and (pre)clinical PET imaging, non-macrocyclic, semi-rigid pentadentate chelators having two N- and three O-donor atoms such as RESCA1 and AMPDA-HB have been proposed with the aim to allow room temperature labelling of temperature-sensitive biomolecules. The paucity of stability data on Al(III) complexes used for PET imaging instigated a complete thermodynamic and kinetic solution study on Al(III) complexes with aminomethylpiperidine (AMP) derivatives AMPTA and AMPDA-HB and the comparison with a RESCA1-like chelator CD3A-Bn (-1,2-diaminocyclohexane--benzyl-,,-triacetic acid).

AAZTA-Like Ligands Bearing Phenolate Arms as Efficient Chelators for Ga Labelling in vitro and in vivo.

The introduction of a phenolate pendant arm in place of an acetate on AAZTA- and DATA-like ligands resulted in hepta- and hexadentate chelators able to form Ga(III) complexes with thermodynamic stability and kinetic inertness higher than that of other Ga(III) complexes based on the parent 6-amino-6-methylperhydro-1,4-diazepine scaffold. In particular, the heptadentate AAZ3A-endoHB with a phenolate arm on an endocyclic N-atom shows a logK of 27.35 and a remarkable resistance to hydroxide coordination up to basic pH (pH>9).

Breeding oat for resistance to the crown rust pathogen Puccinia coronata f. sp. avenae: achievements and prospects.

Crown rust, caused by Puccinia coronata f. sp. avenae (Pca), is a significant impediment to global oat production.

Pre and post stage of infection of Magnaporthe oryzae Oryza in wheat leaves with different resistance levels.

Blast fungus (Magnaporthe oryzae B.C. Couch) is an imminent threat to global food security because it causes serious yield losses in rice (Oryza sativa L.

Brief version of the CAMCOG for illiterate older adults with Alzheimer's dementia.

Background: The Cambridge Cognition Examination (CAMCOG) is one of the most used cognitive assessment batteries for older adults.

Objective: To evaluate a brief version of the CAMCOG for illiterate older adults (CAMCOG-BILL) with Alzheimer's dementia (AD) and healthy controls (CG).

Methods: Cross-sectional case-control study with 246 illiterate older adults (AD [n=159] and CG [n=87], composed by healthy seniors without cognitive complaints) who never attended school or took reading or writing lessons.

Semi-Rigid (Aminomethyl) Piperidine-Based Pentadentate Ligands for Mn(II) Complexation.

Two pentadentate ligands built on the 2-aminomethylpiperidine structure and bearing two tertiary amino and three oxygen donors (three carboxylates in the case of AMPTA and two carboxylates and one phenolate for AMPDA-HB) were developed for Mn(II) complexation. Equilibrium studies on the ligands and the Mn(II) complexes were carried out using pH potentiometry, H-NMR spectroscopy and UV-vis spectrophotometry. The Mn complexes that were formed by the two ligands were more stable than the Mn complexes of other pentadentate ligands but with a lower pMn than Mn(EDTA) and Mn(CDTA) (pMn for Mn(AMPTA) = 7.

A mathematical model of the circadian clock and drug pharmacology to optimize irinotecan administration timing in colorectal cancer.

Scheduling anticancer drug administration over 24 h may critically impact treatment success in a patient-specific manner. Here, we address personalization of treatment timing using a novel mathematical model of irinotecan cellular pharmacokinetics and -dynamics linked to a representation of the core clock and predict treatment toxicity in a colorectal cancer (CRC) cellular model. The mathematical model is fitted to three different scenarios: mouse liver, where the drug metabolism mainly occurs, and two human colorectal cancer cell lines representing an experimental system for human colorectal cancer progression.

Model learning to identify systemic regulators of the peripheral circadian clock.

Motivation: Personalized medicine aims at providing patient-tailored therapeutics based on multi-type data toward improved treatment outcomes. Chronotherapy that consists in adapting drug administration to the patient's circadian rhythms may be improved by such approach. Recent clinical studies demonstrated large variability in patients' circadian coordination and optimal drug timing.

Alcohol Consumption During Pregnancy in Brazil: Elements of an Interpretive Approach.

With this research, we aimed to raise elements to enhance the understanding of alcohol consumption among pregnant women in Brazil. Fourteen women identified as alcohol consumers during pregnancy were interviewed. Alcohol consumption during pregnancy seemed to be associated with three groups of interconnected issues: subjective and individual issues (such as expectations, motivations, and women's difficulty in identifying their own consumption as risky); sociocultural and environmental issues (such as alcohol cultural value, easy access, and influence from relatives, friends, and partners); misinformation, inconsistent opinions publicized through media and lack of technically addressing the subject during prenatal care.

Polymerizable Gd(iii) building blocks for the synthesis of high relaxivity macromolecular MRI contrast agents.

A new synthetic strategy for the preparation of macromolecular MRI contrast agents (CAs) is reported. Four gadolinium(iii) complexes bearing either one or two polymerizable methacrylamide groups were synthesized, serving as monomers or crosslinkers for the preparation of water-soluble, polymeric CAs using Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization. Using this approach, macromolecular CAs were synthesized with different architectures, including linear, hyperbranched polymers and gels.

Rigid and Compact Binuclear Bis-hydrated Gd-complexes as High Relaxivity MRI Agents.

The first binuclear Gd-complex of the 12-membered pyridine-based polyaminocarboxylate macrocyclic ligand PCTA was synthesized by C-C connection of the pyridine units through two different synthetic procedures. A dimeric AAZTA-ligand was also synthesized with the aim to compare the relaxometric results or the two ditopic Gd-complexes. Thus, the H relaxometric study on [Gd PCTA (H O) ] and on [Gd AAZTA (H O) ] highlighted the remarkable rigidity and compactness of the two binuclear complexes, which results in molar relaxivities (per Gd), at 1.

Electrochemical Ring-Opening and -Closing of a Spiropyran.

The bistability of molecular switches is an essential characteristic in their use as functional components in molecular-based devices and machines. For photoswitches, light-driven switching between two stable states proceeds via short-lived changes of the bond order in electronically excited states. Here, bistable switching of a ditertbutyl-substituted spiropyran photoswitch is instead demonstrated by oxidation and subsequent reduction in an overall four-state cycle.

Towards Enhanced MRI Performance of Tumor-Specific Dimeric Phenylboronic Contrast Agents.

It is known that phenylboronic acid (PBA) can target tumor tissues by binding to sialic acid, a substrate overexpressed by cancer cells. This capability has previously been explored in the design of targeting diagnostic probes such as Gd- and Ga-DOTA-EN-PBA, two contrast agents for magnetic resonance imaging (MRI) and positron emission tomography (PET), respectively, whose potential has already been demonstrated through in vivo experiments. In addition to its high resolution, the intrinsic low sensitivity of MRI stimulates the search for more effective contrast agents, which, in the case of small-molecular probes, basically narrows down to either increased tumbling time of the entire molecule or elevated local concentration of the paramagnetic ions, both strategies resulting in enhanced relaxivity, and consequently, a higher MRI contrast.

Hospital admission rate in children and adolescents with mild persistent asthma.

Introduction: The health and financial burden of mild-persistent asthma has been poorly investigated.

Objective: Our aim was to compare the rate of hospital admissions that have occurred during the preceding year between children and adolescents with current mild-persistent (MP) and moderate-severe (MS) asthma.

Methods: We screened children and adolescents with asthma at eight outpatient clinics.