Proximity Effects on the Reactivity of a Nonheme Iron (IV) Oxo Complex in C-H Oxidation.

Precise control of substrate positioning and orientation (its proximity to the reactive unit) is often invoked to rationalize the superior enzymatic reaction rates and selectivities when compared to synthetic models. Artificial nonheme iron (IV) oxo (Fe(IV)=O) complexes react with C(sp)-H bonds via a biomimetic Hydrogen Atom Transfer/Hydroxyl Rebound mechanism, but rates, site-selectivity and even hydroxyl rebound efficiency (ligand rebound versus substrate radical diffusion) are smaller than in oxygenases. Herein, we quantitatively analyze how substrate binding modulates nonheme Fe(IV)=O reactivity by comparing rates and outcomes of C-H oxidation by a pair of Fe(IV)=O complexes that share the same first coordination sphere but only one contains a crown ether receptor that recognizes the substrate.

Efficient Transferase Engineering for SAM Analog Synthesis from Iodoalkanes.

S-Adenosyl-l-methionine (SAM) is an important cosubstrate in various biochemical processes, including selective methyl transfer reactions. Simple methods for the (re)generation of SAM analogs could expand the chemistry accessible with SAM-dependent transferases and go beyond methylation reactions. Here we present an efficient enzyme engineering strategy to synthesize different SAM analogs from "off-the-shelf" iodoalkanes through enzymatic alkylation of S-adenosyl-l-homocysteine (SAH).

Lipidomics Reveals Myocardial Lipid Composition in a Murine Model of Insulin Resistance Induced by a High-Fat Diet.

Ectopic fat accumulation in non-adipose tissues is closely related to diabetes-related myocardial dysfunction. Nevertheless, the complete picture of the lipid metabolites involved in the metabolic-related myocardial alterations is not fully characterized. The aim of this study was to characterize the specific lipid profile in hearts in an animal model of obesity/insulin resistance induced by a high-fat diet (HFD).

Assessing the Fate of Benzophenone-Type UV Filters and Transformation Products during Soil Aquifer Treatment: The Biofilm Compartment as Bioaccumulator and Biodegrader in Porous Media.

The fate of selected UV filters (UVFs) was investigated in two soil aquifer treatment (SAT) systems, one supplemented with a reactive barrier containing clay and vegetable compost and the other as a traditional SAT reference system. We monitored benzophenone-3 (BP-3) and its transformation products (TPs), including benzophenone-1 (BP-1), 4,4'-dihydroxybenzophenone (4DHB), 4-hydroxybenzophenone (4HB), and 2,2'-dihydroxy-4-methoxybenzophenone (DHMB), along with benzophenone-4 (BP-4) and avobenzone (AVO) in all involved compartments (water, aquifer sediments, and biofilm). The reactive barrier, which enhances biochemical activity and biofilm development, improved the removal of all detected UVFs in water samples.

Personalized strategies for academic success in learning anatomy: Exploring metacognitive and technological adaptation in medical students.

Personalization of learning is an educational strategy rooted in metacognition and is significant in academic training. This is especially true in medical contexts. This study explored the relationship between the metacognitive profile of students of human anatomy, the classification of questions according to their difficulty, and the anatomical domain.

CD200 genotype is associated with clinical outcome of patients with multiple myeloma.

Immune dysfunction in patients with MM affects both the innate and adaptive immune system. Molecules involved in the immune response pathways are essential to determine the ability of cancer cells to escape from the immune system surveillance. However, few data are available concerning the role of immune checkpoint molecules in predicting the myeloma control and immunological scape as mechanism of disease progression.

Positive mental health and sense of coherence among emergency medical service professionals.

Background: Positive mental health (PMH) is a construct used to define and evaluate health from a positive perspective. Healthcare professionals in the emergency ambulance service are more likely to experience mental health disorders than the overall population. The demographic and occupational variables and Sense of Coherence (SOC) can act as predictors of PMH and can serve as protective elements against stress and demanding situations in the work environment.

Recurrent alcohol-associated hepatitis is common and is associated with increased mortality.

Background And Aims: Alcohol relapse after surviving an episode of alcohol-associated hepatitis (AH) is common. However, the clinical features, risk factors, and prognostic implications of recurrent alcohol-associated hepatitis (RAH) are not well described.

Approach And Results: A registry-based study was done of patients admitted to 28 Spanish hospitals for an episode of AH between 2014 and 2021.

Mechanistic insights on the antibacterial action of the kyotorphin peptide derivatives revealed by in vitro studies and Galleria mellonella proteomic analysis.

Objectives: The selected kyotorphin derivatives were tested to improve their antimicrobial and antibiofilm activity. The antimicrobial screening of the KTP derivatives were ascertained in the representative strains of bacteria, including Streptococcus pneumoniae, Streptococcus pyogenes, Escherichia coli and Pseudomonas aeruginosa.

Methods: Kyotorphin derivatives, KTP-NH, KTP-NH-DL, IbKTP, IbKTP-NH, MetKTP-DL, MetKTP-LD, were designed and synthesized to improve lipophilicity and resistance to enzymatic degradation.

The shortest path method (SPM) webserver for computational enzyme design.

SPMweb is the online webserver of the Shortest Path Map (SPM) tool for identifying the key conformationally-relevant positions of a given enzyme structure and dynamics. The server is built on top of the DynaComm.py code and enables the calculation and visualization of the SPM pathways.

Gestural communication in wild spider monkeys (Ateles geoffroyi).

Gestures play a central role in the communication systems of several animal families, including primates. In this study, we provide a first assessment of the gestural systems of a Platyrrhine species, Geoffroy's spider monkeys (Ateles geoffroyi). We observed a wild group of 52 spider monkeys and assessed the distribution of visual and tactile gestures in the group, the size of individual repertoires and the intentionality and effectiveness of individuals' gestural production.

Streptococcal quorum sensing peptide CSP-7 contributes to muscle inflammation and wasting.

Muscle wasting diseases, such as cancer cachexia and age-associated sarcopenia, have a profound and detrimental impact on functional independence, quality of life, and survival. Our understanding of the underlying mechanisms is currently limited, which has significantly hindered the development of targeted therapies. In this study, we explored the possibility that the streptococcal quorum sensing peptide Competence Stimulating Peptide 7 (CSP-7) might be a previously unidentified contributor to clinical muscle wasting.

Targeting dihydroceramide desaturase 1 (Des1): Syntheses of ceramide analogues with a rigid scaffold, inhibitory assays, and AlphaFold2-assisted structural insights reveal cyclopropenone PR280 as a potent inhibitor.

Dihydroceramide desaturase 1 (Des1) catalyzes the formation of a CC double bond in dihydroceramide to furnish ceramide. Inhibition of Des1 is related to cell cycle arrest and programmed cell death. The lack of the Des1 crystalline structure, as well as that of a close homologue, hampers the detailed understanding of its inhibition mechanism and difficults the design of new inhibitors, thus making Des1 a strategic target.

Unraveling the gut-brain connection: The association of microbiota-linked structural brain biomarkers with behavior and mental health.

Aim: The gut microbiota can influence human behavior. However, due to the massive multiple-testing problem, research into the relationship between microbiome ecosystems and the human brain faces drawbacks. This problem arises when attempting to correlate thousands of gut bacteria with thousands of brain voxels.

"Ethnic disparities in the prevalence of Molar-Incisor-Hypomineralisation (MIH) and caries among 6-12-year-old children in Catalonia, Spain".

Aim: To study the prevalence of MIH and caries in 6- and 12-year-old schoolchildren and their association with ethnic disparities and other relevant factors.

Background: In recent years, there has been uneven improvement in school children's oral health, highlighting inequalities in access to dental care and health outcomes, particularly among ethnic minorities. The most prevalent oral disease in childhood, caries, is preventable, as its risk factors are well known.

From Stilbenes to carbo-Stilbenes: an Encouraging Prospect.

Beyond previously described carbo-naphthalene and carbo-biphenyl, a novel type of bis-carbo-benzenic molecules is envisaged from the stilbene parent. The synthesis, structure, spectroscopic and electrochemical properties of two such carbo-stilbenes are described at complementary experimental and computational DFT levels. In the selected targets, the bare skeletal carbo-mer of carbo-stilbene is decorated by 8 or 10 phenyl groups, 0 or 2 tert-butyl groups, and 2 n-octyl chains, the later substituents being introduced to compensate anticipated solubility issues.

Outcomes and factors associated with relapse of vaccine-induced liver injury after SARS CoV-2 immunization: A nationwide study.

Introduction And Objectives: Different patterns of liver injury have been reported in association with the SARS-CoV-2 vaccines. The aim of this study was to describe a nationwide cohort of patients with SARS CoV-2 vaccine-induced liver injury, focusing on treatment and the evolution after further booster administration.

Patients And Methods: multicentre, retrospective-prospective study, including subjects who developed abnormal liver tests within 90 days after administration of SARS-CoV-2 vaccination.

Influence of seagrass meadow length on beach morphodynamics: An experimental study.

A novel flume experiment was conducted to compare the sheltering effect of surrogate seagrass meadows of two different lengths against a bare beach (benchmark). The analyses focused on assessing the impact of meadow cross-shore extent on wave height attenuation, behaviour of wave orbital velocity components, sediment transport, and shoreline erosion. Throughout the tests conducted in the large-scale CIEM wave flume at LIM/UPC Barcelona, meadow density and submergence ratio remained constant, while irregular waves were run over an initial 1:15 sand beach profile.

Atlantic bonito (Sarda) genomic analysis reveals population differentiation across Northeast Atlantic and mediterranean locations: Implications for fishery management.

The Atlantic bonito (Sarda, family Scombridae) is a pelagic species and one of the most exploited small tuna species. Despite its economic importance, biological information is scarce with no associated management directives. In this study, using a population genomic approach resulted in a lack of panmixia of two genetic pools with different effective population sizes (east central-tropical Atlantic and northeast Atlantic-Mediterranean) and an intermixing zone in Atlantic Morocco.

Effect of 5-Alpha Reductase Inhibitors on Magnetic Resonance Imaging and Prostate Cancer Detection.

Concerns exist regarding the effects of 5-alpha reductase inhibitors (5-ARIs) on multipa-rametric magnetic resonance imaging (mpMRI) and clinically significant prostate cancer (csPCa) detection. Our objective is to analyze the effect of 5-ARI on the prostate imaging-reporting and data system (PI-RADS) distribution and csPCa and insignificant PCa (iPCa) detection. Among 2212 men with serum prostate-specific antigen levels of >3.

Associations Between Patient Comfort with a Primary Care Provider and Three Measures of Behavioral Health Services Utilization.

Background: Behavioral health services (BHS) can help improve and treat mental and emotional health problems. Yet, attitudinal and/or structural barriers often prevent individuals from accessing and benefiting from these services. Positive provider-patient interactions in healthcare, encompassing patient comfort with a primary care provider (PCP), which is often enhanced by shared decision-making, may mitigate the stigma associated with seeing a mental health professional; this may improve BHS utilization among patients who need these services.