Strong adsorption of guanidinium cations to the air-water interface.

Combining Deep-UV second harmonic generation spectroscopy with molecular simulations, we confirm and quantify the specific adsorption of guanidinium cations to the air-water interface. Using a Langmuir analysis of measurements at multiple concentrations, we extract the Gibbs free energy of adsorption, finding it larger than typical thermal energies. Molecular simulations clarify the role of polarizability in tuning the thermodynamics of adsorption, and establish the preferential parallel alignment of guanidinium at the air-water interface.

A Detailed Reaction Mechanism for Thiosulfate Oxidation by Ozone in Aqueous Environments.

The ozone oxidation, or ozonation, of thiosulfate is an important reaction for wastewater processing, where it is used for remediation of mining effluents, and for studying aerosol chemistry, where its fast reaction rate makes it an excellent model reaction. Although thiosulfate ozonation has been studied since the 1950s, challenges remain in developing a realistic reaction mechanism that can satisfactorily account for all observed products with a sequence of elementary reaction steps. Here, we present novel measurements using trapped microdroplets to study the pH-dependent thiosulfate ozonation kinetics.

Replacement of the essential nitro group by electrophilic warheads towards nitro-free antimycobacterial benzothiazinones.

Nitrobenzothiazinones (BTZs) are undergoing late-stage development as a novel class of potent antitubercular drug candidates with two compounds in clinical phases. BTZs inhibit decaprenylphosphoryl-β-d-ribose oxidase 1 (DprE1), a key enzyme in cell wall biosynthesis of mycobacteria. Their mechanism of action involves an in-situ-reduction of the nitro moiety to a reactive nitroso intermediate capable of covalent binding to Cys387 in the catalytic cavity.

Modulation of the Meisenheimer complex metabolism of nitro-benzothiazinones by targeted C-6 substitution.

Tuberculosis, caused by Mycobacterium tuberculosis, remains a major public health concern, demanding new antibiotics with innovative therapeutic principles due to the emergence of resistant strains. Benzothiazinones (BTZs) have been developed to address this problem. However, an unprecedented in vivo biotransformation of BTZs to hydride-Meisenheimer complexes has recently been discovered.

Time-Resolved X-ray Emission Spectroscopy and Resonant Inelastic X-ray Scattering Spectroscopy of Laser Irradiated Carbon.

The existence of liquid carbon as an intermediate phase preceding the formation of novel carbon materials has been a point of contention for several decades. Experimental observation of such a liquid state requires nonthermal melting of solid carbon materials at various laser fluences and pulse properties. Reflectivity experiments performed in the mid-1980s reached opposing conclusions regarding the metallic or insulating properties of the purported liquid state.

Order-to-Disorder Transition and Hydrogen Bonding in the Jahn-Teller Active NHCrF Fluoroperovskite.

Large quantities of high-purity NHCrF have been synthesized using a wet-chemical method, and its structural chemistry and magnetic properties are investigated in detail for the first time. NHCrF is a tetragonal fluoroperovskite that displays an ordering of the ammonium (NH) groups at room temperature and C-type orbital ordering. The ammonium groups order and display distinct signs of hydrogen bonds to nearby fluoride anions by buckling the Cr-F-Cr angle away from 180°.

Spiers Memorial Lecture: Water at interfaces.

In this article we discuss current issues in the context of the four chosen subtopics for the meeting: dynamics and nano-rheology of interfacial water, electrified/charged aqueous interfaces, ice interfaces, and soft matter/water interfaces. We emphasize current advances in both theory and experiment, as well as important practical manifestations and areas of unresolved controversy.

Maximum stem diameter predicts liana population demography.

Determining population demographic rates is fundamental to understanding differences in species' life-history strategies and their capacity to coexist. Calculating demographic rates, however, is challenging and requires long-term, large-scale censuses. Body size may serve as a simple predictor of demographic rate; can it act as a proxy for demographic rate when those data are unavailable? We tested the hypothesis that maximum body size predicts species' demographic rate using repeated censuses of the 77 most common liana species on the Barro Colorado Island, Panama (BCI) 50-ha plot.

Design and synthesis of benzofuran- and naphthalene-fused thiazinones as antimycobacterial agents.

Benzothiazinones (BTZs) have widely inspired medicinal chemistry and translational research due to their remarkable antitubercular potency and clinical potential. While most structure-activity relationship campaigns have largely focused on lateral chain modifications and substituents on the BTZ core, scaffold hopping strategies have been rarely investigated previously. In this work, we report the first example of ring expansion of the BTZ core toward benzofuran- and naphthalene-fused thiazinones.

Comprehensive interrogation of gene lists from genome-scale cancer screens with oncoEnrichR.

Genome-scale screening experiments in cancer produce long lists of candidate genes that require extensive interpretation for biological insight and prioritization for follow-up studies. Interrogation of gene lists frequently represents a significant and time-consuming undertaking, in which experimental biologists typically combine results from a variety of bioinformatics resources in an attempt to portray and understand cancer relevance. As a means to simplify and strengthen the support for this endeavor, we have developed oncoEnrichR, a flexible bioinformatics tool that allows cancer researchers to comprehensively interrogate a given gene list along multiple facets of cancer relevance.

A QSAR Study for Antileishmanial 2-Phenyl-2,3-dihydrobenzofurans .

Leishmaniasis, a parasitic disease that represents a threat to the life of millions of people around the globe, is currently lacking effective treatments. We have previously reported on the antileishmanial activity of a series of synthetic 2-phenyl-2,3-dihydrobenzofurans and some qualitative structure-activity relationships within this set of neolignan analogues. Therefore, in the present study, various quantitative structure-activity relationship (QSAR) models were created to explain and predict the antileishmanial activity of these compounds.

Transgastric laparoscopic polypectomy in giant gastric polyps not susceptible of endoscopic management: novel surgical technique and case series.

Background: The identification of gastric polyps incidentally in endoscopies of the upper digestive tract has increased its incidence, varying between 0.5% and 23%. 10% of these polyps have symptoms, 40% are hyperplastic.

Top-down modulation impairs priming susceptibility in complex decision-making with social implications.

Could social context variables prime complex decisions? Could top-down processes impair this priming susceptibility? Complex decisions have been mainly studied from economic and moral perspectives, and Dual Process Theories provide evidence of how these processes could be affected. To address these issues from a political perspective, online experiments were conducted. Participants (n = 252) were asked to choose a face from 4 options, each associated with different frequencies (repetition priming) or with phrases with different emotional valence (emotional priming), for an unspecified task (UST group) or an important task (IMT group).

Natural products in antibiotic development: is the success story over?

Natural product (NP)-based antibiotics have been exploited for more than eighty years and continue saving uncountable lives every year. However, antimicrobial R&D is inadequate to counteract antimicrobial resistance. The majority of marketed antibiotics are inspired by NP classes that were discovered more than 50 years ago.

GC/MS-Based Fingerprinting Reveals Two Chemotypes in the Leaf Essential Oils from Magnolia grandiflora Trees within The Urban Forestry of a Colombian Andean Plateau.

Magnolia grandiflora is an aromatic plant widely distributed around the world. In Colombia, and more specifically in Bogotá, M. grandiflora has been introduced as part of urban forestry programs, and their specimens are therefore subjected to several environments.

Laparoendoscopic surgery for the treatment of gastrointestinal stromal tumors: A case series.

Introduction: Gastrointestinal stromal tumors (GISTs) are the most common mesenchymal neoplasms of the gastrointestinal tract. The standard management for localized GIST is the complete surgical resection. For this procedure, laparoendoscopic cooperative surgery (LECS) has been proposed as a safe and effective alternative.

RpoN-Based stapled peptides with improved DNA binding suppress virulence.

Stapled peptides have the ability to mimic α-helices involved in protein binding and have proved to be effective pharmacological agents for disrupting protein-protein interactions. DNA-binding proteins such as transcription factors bind their cognate DNA sequences an α-helix interacting with the major groove of DNA. We previously developed a stapled peptide based on the bacterial alternative sigma factor RpoN capable of binding the RpoN DNA promoter sequence and inhibiting RpoN-mediated expression in .

Composition and Antifungal Activity of the Alkaloidal Fraction of Leaves: A Biochemometrics-Based Exploration.

plants are well-recognized due to their significant alkaloid content, which has made them the subject of several studies. However, the lack of chemical and biological information on the Colombian species remains a fact. Therefore, the alkaloidal fractions from the leaves of L.

Development of Predictive Classification Models for Whole Cell Antimycobacterial Activity of Benzothiazinones.

Nitrobenzothiazinones (BTZs) are a very potent class of antibiotics against . However, relationships between their structural properties and whole cell activity remain poorly predictable. Herein, we present the synthesis and antimycobacterial evaluation of a diverse set of BTZs.

The Tyrosine Phosphatase hPTPRβ Controls the Early Signals and Dopaminergic Cells Viability via the P2X Receptor.

ATP, one of the signaling molecules most commonly secreted in the nervous system and capable of stimulating multiple pathways, binds to the ionotropic purinergic receptors, in particular, the P2X receptor (P2XR) and stimulates neuronal cell death. Given this effect of purinergic receptors on the viability of dopaminergic neurons model cells and that Ras GTPases control Erk1/2-regulated mitogen-activated cell proliferation and survival, we have investigated the role of the small GTPases of the Ras superfamily, together with their regulatory and effector molecules as the potential molecular intermediates in the P2XR-regulated cell death of SN4741 dopaminergic neurons model cells. Here, we demonstrate that the neuronal response to purinergic stimulation involves the Calmodulin/RasGRF1 activation of the small GTPase Ras and Erk1/2.

Pre- and in-hospital anticoagulation therapy in coronavirus disease 2019 patients: a propensity-matched analysis of in-hospital outcomes.

Aims: To estimate if chronic anticoagulant (CAC) treatment is associated with morbidity and mortality outcomes of patients hospitalized for SARS-CoV-2 infection.

Methods: In this European multicentric cohort study, we included 1186 patients of whom 144 were on CAC (12.1%) with positive coronavirus disease 2019 testing between 1 February and 30 July 2020.

Quantitative Structure-Activity Relationships of Natural-Product-Inspired, Aminoalkyl-Substituted 1-Benzopyrans as Novel Antiplasmodial Agents.

On the basis of the finding that various aminoalkyl-substituted chromene and chromane derivatives possess strong and highly selective in vitro bioactivity against , the pathogen responsible for tropical malaria, we performed a structure-activity relationship study for such compounds. With structures and activity data of 52 congeneric compounds from our recent studies, we performed a three-dimensional quantitative structure-activity relationship (3D-QSAR) study using the comparative molecular field analysis (CoMFA) approach as implemented in the Open3DQSAR software. The resulting model displayed excellent internal and good external predictive power as well as good robustness.