Automated Synthesis of C1-Functionalized Oligosaccharides.

Automated glycan assembly (AGA) streamlines the synthesis of complex oligosaccharides. The reducing end of the oligosaccharide serves as an attachment site to the polymer support to liberate a free reducing end or an aminopentanol for ready conjugation to carrier proteins or surfaces. The facile installation of different aglycons on oligosaccharides has not been possible via AGA until now.

Microplastics Generate Less Mineral Protection of Soil Carbon and More CO Emissions.

Microplastic pollution in terrestrial ecosystems threatens to destabilize large soil carbon stocks that help to mitigate climate change. Carbon-based substrates can release from microplastics and contribute to terrestrial carbon pools, but how these emerging organic compounds influence carbon mineralization and sequestration remains unknown. Here, microcosm experiments are conducted to determine the bioavailability of microplastic-derived dissolved organic matter (MP-DOM) in soils and its contribution to mineral-associated carbon pool.

Rare-Earth Substitution Induced Symmetry Breaking for The First Sc-Based Nonlinear Optical Chalcogenide with High-Performance.

Chalcogenides are the most important infrared nonlinear optical (NLO) material candidates, and the exploration of high-performance ones is attractive and challengeable. Hitherto, there is no NLO scandium (Sc) chalcogenides experimentally studied. Here, new quaternary Sc thiophosphate CsScPS (CSPS) was synthesized by the facile metal oxide-boron-sulfur/reactive flux hybrid solid-state method.

Polyethyleneimine-Based Cryogels Enabling the Selective and Reversible Adsorption of Chlorine.

Herein hyperbranched polyethyleneimine (hPEI) cryogels are reported for the selective and reversible adsorption of elemental chlorine. The cryogels are prepared in an aqueous solution by crosslinking with glutaraldehyde at subzero temperatures. The final macroporous composites bearing ammonium chloride groups are obtained after freeze-drying.

Scoliosis development in 5q-spinal muscular atrophy under disease modifying therapies.

Purpose: 5q-spinal muscular atrophy (SMA) is a treatable neuromuscular disorder associated with scoliosis in up to 90% of patients. New SMA therapies could mark a paradigm shift in scoliosis management, but their effects on scoliosis development remain unclear. This study aims to observe scoliosis progression in the current treatment landscape to inform management strategies.

Integrative determination of atomic structure of mutant huntingtin exon 1 fibrils implicated in Huntington disease.

Neurodegeneration in Huntington's disease (HD) is accompanied by the aggregation of fragments of the mutant huntingtin protein, a biomarker of disease progression. A particular pathogenic role has been attributed to the aggregation-prone huntingtin exon 1 (HTTex1), generated by aberrant splicing or proteolysis, and containing the expanded polyglutamine (polyQ) segment. Unlike amyloid fibrils from Parkinson's and Alzheimer's diseases, the atomic-level structure of HTTex1 fibrils has remained unknown, limiting diagnostic and treatment efforts.

Hydrogen Bond Blueshifts in Nitrile Vibrational Spectra Are Dictated by Hydrogen Bond Geometry and Dynamics.

Vibrational Stark effect (VSE) spectroscopy has become one of the most important experimental approaches to determine the strength of noncovalent, electrostatic interactions in chemistry and biology and to quantify their influence on structure and reactivity. Nitriles (C≡N) have been widely used as VSE probes, but their application has been complicated by an anomalous hydrogen bond (HB) blueshift which is not encompassed within the VSE framework. We present an empirical model describing the anomalous HB blueshift in terms of H-bonding geometry, i.

Efficacy and working mechanisms of a Go/No-Go task-based inhibition training in smoking: A randomized-controlled trial.

Objective: Deficits in inhibitory control contribute to smoking behavior. Inhibitory control training (ICT), which involves repeatedly inhibiting responses to general or substance-related stimuli, shows promise in reducing problematic substance use. This preregistered randomized-controlled trial is the first to investigate the efficacy of general and smoking-specific Go/No-Go task-based ICT on smoking behavior compared to control groups receiving no ICT.

An improved matrix deposition technique for thin layer chromatography coupled to MALDI-TOF mass spectrometry (TLC-MALDI).

Analytical thin layer chromatography (TLC) is a simple yet powerful chromatographic technique that is widely used for the qualitative characterization of complex mixtures such as plant extracts. For their qualitative and visual characterisation, a large number of more or less specific colour reactions are at hand and numerous reference substances are available as well. However, the identification of extract components by colour and the comparison of retention times is not straightforward.

Legacy effects of an invasive legume more strongly impact bacterial than plant communities in a Mediterranean-type ecosystem.

The impacts of invasive plants on ecosystem processes and functions may persist as "legacy effects" after their removal. Understanding these effects on native plant-soil interactions is critical for guiding ecological restoration efforts. This study examines the legacy effects of the invasive legume Acacia saligna (Labill.

Klebsiella pneumoniae Glycoconjugate Vaccine Leads Based on Semi-Synthetic O1 and O2ac Antigens.

Klebsiella pneumoniae (KP) is a common opportunistic pathogen that emerged as a new critical threat to human health, due to its hypervirulence and widespread resistance against many antibiotics, including carbapenems. Alternative intervention strategies such as vaccines are not available. Cell-surface lipopolysaccharides (LPS) and capsular polysaccharides (CPS) are attractive targets for vaccine development.

Does Students' Level of Intelligence Moderate the Relationship Between Socio-Economic Status and Academic Achievement?

The association between school students' social background and school achievement is well documented. Recent studies demonstrated that this association might be moderated by the level of cognitive potential. Based on these results, we recruited an elementary school sample ( = 837) and an adolescent sample at the end of their compulsory school time ( = 2100) to investigate whether the associations between students' social background and their academic achievement in math and language arts were moderated by the level of their general cognitive competencies, i.

Upgrading the Bioinspired Iron-Polyporphyrin Structures by Abiological Metals Toward New-Generation Reactive Oxygen Biocatalysts.

Developing artificial enzymes based on organic molecules or polymers for reactive oxygen biocatalysis has broad applicability. Here, inspired by heme-based enzyme systems, we construct the abiological iron group metal-based polyporphyrin (Ru/Os-coordinated porphyrin-based biocatalyst, Ru/Os-PorBC) to serve as a new generation of efficient and versatile reactive oxygen species (ROS)-related biocatalyst. Due to the structural benefits, including excellent electron configuration, appropriate bandgap, and optimized adsorption and activation of reaction intermediates, Ru/Os-PorBC shows unparalleled ROS-production activities regarding maximum reaction rate and turnover numbers, which also demonstrates superior pH and temperature adaptability compared to natural enzymes.

Tire Wear Particles Exposure Enhances Denitrification in Soil by Enriching Labile DOM and Shaping the Microbial Community.

Tire wear particles (TWP) are emerging contaminants in the soil environment due to their widespread occurrence and potential threat to soil health. However, their impacts on soil biogeochemical processes remain unclear. Here, we investigated the effects of TWP at various doses and their leachate on soil respiration and denitrification using a robotized continuous-flow incubation system in upland soil.

Synergistic Ultrasound-Activable Artificial Enzyme and Precision Gene Therapy to Suppress Redox Homeostasis and Malignant Phenotypes for Controllably Combating Hepatocellular Carcinoma.

Hepatocellular carcinoma (HCC) remains one of the most lethal malignant tumors. Multimodal therapeutics with synergistic effects for treating HCC have attracted increasing attention, for instance, designing biocompatible porphyrin-based nanomedicines for enzyme-mimetic and ultrasound (US)-activable reactive oxygen species (ROS) generation. Despite the promise, the landscape of such advancements remains sparse.

π-Lewis Base Activation of Carbonyls and Hexafluorobenzene.

We report hitherto elusive side-on η-bonded palladium(0) carbonyl (anthraquinone, benzaldehyde) and arene (benzene, hexafluorobenzene) palladium(0) complexes and present the catalytic hydrodefluorination of hexafluorobenzene by cyclohexene. The comparison with respective cyclohexene, pyridine and tetrahydrofuran complexes reveals that the experimental ligand binding strengths follow the order THF View Article and Find Full Text PDF

Antigen presentation by MHC-II is shaped by competitive and cooperative allosteric mechanisms of peptide exchange.

Major histocompatibility complex class II (MHC-II) presents antigens to T helper cells. The spectrum of presented peptides is regulated by the exchange catalyst human leukocyte antigen DM (HLA-DM), which dissociates peptide-MHC-II complexes in the endosome. How susceptible a peptide is to HLA-DM is mechanistically not understood.

Vanadium single-atoms coordinated artificial peroxidases as biocatalyst-linked immunosorbent assay for highly-sensitive carcinoembryonic antigen immunoassay.

In medical and biomedical fields, enzyme-mimetic nanomaterials have garnered significant interest as efficacious signal enhancers for biocatalyst-linked immunosorbent assays (BLISA). Despite the burgeoning enthusiasm, engineering artificial biocatalysts that exhibit both exceptional catalytic proficiency and pronounced colorimetric signal output remains a formidable challenge. Inspired by the heme structures and biocatalytic activities of horseradish peroxidase, we introduce the synthesis of vanadium single-atoms (SAV) coordinated artificial peroxidases as BLISA for highly sensitive and selective carcinoembryonic antigen (CEA) immunoassay.

Fit for purpose? Evaluating benthic invertebrate DNA metabarcoding for ecological status class assessment in streams under the Water Framework Directive.

The ecological state of aquatic ecosystems is systematically monitored using various bioindicators in many countries worldwide. In the European Union, freshwater biomonitoring is the central component of the EU Water Framework Directive (WFD, 2000/60/EC) and currently based on morpho-taxonomic methods. DNA metabarcoding is a novel approach to assess the ecological state fast and efficiently based on organismal DNA signatures and thereby support and upscale biomonitoring.

Increased methane production associated with community shifts towards Methanocella in paddy soils with the presence of nanoplastics.

Background: Planetary plastic pollution poses a major threat to ecosystems and human health in the Anthropocene, yet its impact on biogeochemical cycling remains poorly understood. Waterlogged rice paddies are globally important sources of CH. Given the widespread use of plastic mulching in soils, it is urgent to unravel whether low-density polyethylene (LDPE) will affect the methanogenic community in flooded paddy soils.

Reinvestigation of the mechanism of dioxygen activation at a Mn(cyclam) center.

This study deals with the unprecedented reactivity of a [(cyclam)Mn(OTf)] (3-cis; OTf = CFSO) with O, which, depending on the presence or absence of a hydrogen atom donor like 1-hydroxy-2,2,6,6-tetramethyl-piperidine (TEMPO-H), selectively generates di-μ-oxo Mn(III)Mn(IV) (1) or Mn (2) complexes, respectively. Both dimers have been characterized by different techniques including single-crystal X-ray diffraction, X-ray absorption spectroscopy, and electron paramagnetic resonance. Oxygenation reactions carried out with labeled O and Resonance Raman spectroscopy unambiguously show that the oxygen atoms present in the MnMn dimer originate from O.

Navigating Illumina DNA methylation data: biology versus technical artefacts.

Illumina-based BeadChip arrays have revolutionized genome-wide DNA methylation profiling, pushing it into diagnostics. However, comprehensive quality assessment remains challenging within a wide range of available tissue materials and sample preparation methods. This study tackles two critical issues: differentiating between biological effects and technical artefacts in suboptimal quality samples and the impact of the first sample on the Illumina-like normalization algorithm.

Exploring transcription modalities from bimodal, single-cell RNA sequencing data.

There is a growing interest in generating bimodal, single-cell RNA sequencing (RNA-seq) data for studying biological pathways. These data are predominantly utilized in understanding phenotypic trajectories using RNA velocities; however, the shape information encoded in the two-dimensional resolution of such data is not yet exploited. In this paper, we present an elliptical parametrization of two-dimensional RNA-seq data, from which we derived statistics that reveal four different modalities.

Synthetic chitin oligosaccharide nanocrystals and their higher-order assemblies.

Self-assembly is a powerful strategy for creating complex architectures and elucidating the aggregation behaviors of biopolymers. Herein, we investigate the hierarchical assembly of chitin using a approach based on synthetic oligosaccharides. We discovered that chitin oligosaccharides self-assemble into platelets, which then form higher-order structures.