Aryl bis(imino)acenaphthenes (Ar-BIANs) are well-established rigid and sterically bulky diimine ligands, which are redox-noninnocent and versatile π-acceptors due to their low-lying π* orbitals and ...are frequently used to bind transition metals. However, the coordination chemistry of Ar-BIAN ligands to main group elements is not as well-developed as that of their transition metal counterparts. In particular, there are no comprehensive studies describing the spectroscopic and electrochemical properties of main group Ar-BIAN complexes. Herein, we report the synthesis and full characterization of a series of new indium(III) Ar-BIAN complexes, bearing 2,6-dialkyl (1b and 2b), 4-nitro (3b), and 4-dimethylamino (4b) groups at the aryl-diimine part of the ligand. Their optical and electrochemical properties have been revealed by UV–vis spectroscopy and cyclic voltammetry, respectively. Additionally, DFT calculations were performed to gain insights into the nature of the properties displayed.
The aim of our study was to evaluate the diagnostic performance of two antigen rapid diagnostic tests (Ag‐RDTs) to diagnose severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) infection. We ...evaluated Panbio and SD‐Biosensor Ag‐RDTs. We employed 186 polymerase chain reaction (PCR) negative samples to evaluate the specificity and 170 PCR positive samples to assess the sensitivity. We evaluated their sensitivity according to Cycle threshold (C
t) values and days post onset of symptoms (d.p.o.). Tests were compared using the McNemar's test. Agreement was evaluated using the kappa score. Specificity was 100% for Panbio and 97.3% for SD‐Biosensor. Sensitivity for samples with C
t ≤ 20 was 100% for both assays and for samples with C
t = 20–25 was 93.0% (Panbio) and 95.3% (SD‐Biosensor) (p = 1.000). Sensitivity decreased for samples wit C
t = 25–30 (Panbio: 41.3%, SD‐Biosensor: 52.2%, p = 0.125) and samples with C
t ≥ 30 (Panbio: 5.0%, SD‐Biosensor: 17.5%, p = 0.063). Sensitivity within seven d.p.o. was 87.7% for Panbio and 90.4% for SD‐Biosensor and notably decreased after seven d.p.o. Agreement with PCR was excellent for high viral load samples (C
t ≤ 25): Panbio, 98.9%, kappa = 0.974; SD‐Biosensor, 97.4%, kappa = 0.940. Agreement between Ag‐RDTs was excellent (94.9%, kappa = 0.882). Panbio and SD‐Biosensor Ag‐RDTs showed excellent agreement and diagnostic performance results for samples with high viral loads (C
t ≤ 25) or samples within seven d.p.o.
Highlights
Panbio and SD‐Biosensor Ag‐RDTs are reliable to diagnose SARS‐CoV‐2 infection.
They showed high specificity: 100% (Panbio) and 97.3% (SD‐Biosensor).
Sensitivity for samples with Ct ≤ 20 was 100% and for samples with Ct ≤ 25 was over 93%.
Their sensitivity was over 87% within 7 days after symptoms onset. Agreement between them was excellent (agreement = 94.9%, kappa = 0.882).
Mechanochemistry has been established to be an environmentally-friendly way of conducting reactions in a solvent-free manner. The development of mechanochemical orthogonal reactions, in which ...multiple reagents are milled together, can be a powerful strategy to selectively yield the desired product. Such orthogonal syntheses are rare, especially those involving main group frameworks - based on bonds other than carbon - which are yet to be reported. Herein, we demonstrate the direct formation of air- and moisture-stable cyclophosph(v)azanes enabled by an orthogonal "one-step one-pot" mechanochemical reaction. In addition, detailed hydrolytic- and air-stability studies, conducted over one and 12 months, respectively, revealed high robustness of these compounds.
A simple low cost method permits controlled, reproducible doping of TiO2 anatase by boron. The resulting materials exhibit red-shifted absorption spectra and unprecedented photocatalytic activity ...under visible light. XP spectra are consistent with the presence of “active” and “inactive” forms of B corresponding to substitutional boron and boric oxide-like material, respectively.
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•A series of novel metal-selenide/MXene composites are designed for Li/Na storage.•These composites with MXene supporting framework are rich in meso- and macropores.•A ...selenium-vacancy rich CoSe2@C/MXene composite is synthesized by ball-milling.•This avoids critical preparation and storage condition for few-layered MXenes.•The process reported shows a much lower environmental footprint and energy cost.
The development of new energy-related materials is the pinnacle to attaining a sustainable society based on renewable energy. Over the past decades, plenty of electrode materials have been investigated seeking better energy storage properties. However, the often-tedious synthetic procedures and large amounts of solvents utilised during their syntheses incur high costs and severe environmental pollution. Here we present a solvent-free approach to metal–organic-frameworks/MXene-derived carbonaceous metal selenide/MXene composites with unique nanostructures rich in mesopores and macropores. These species can be readily transformed into high-performance electrode materials with enhanced Li/Na ion storage properties compared with their solution-based counterparts. Herein we report not only a unique metal–organic framework/MXene-derived electrode material displaying high-performance for advanced lithium/sodium storage applications but also its novel environmentally benign production process.
The transition‐metal‐catalyzed 2+2+2 cycloaddition of nitriles and alkynes is an established synthetic approach to pyridines; however, these cycloadditions often rely on the use of tethered diynes or ...cyanoalkynes as one of the reactants. Thus, examples of efficient, fully intermolecular catalytic 2+2+2 pyridine synthesis, especially those employing unactivated nitriles and internal alkynes leading to pentasubstituted pyridines, remain scarce. Herein, we report on simple and inexpensive catalytic systems based on cobalt(II) iodide, 1,3‐bis(diphenylphosphino)propane, and Zn that promote 2+2+2 cycloaddition of various nitriles and diarylacetylenes for the synthesis of a broad range of polyarylated pyridines. DFT studies support a reaction pathway involving oxidative coupling of two alkynes, insertion of the nitrile into a cobaltacyclopentadiene, and C‐N reductive elimination. The resulting tetra‐ and pentaarylpyridines serve as precursors to hitherto unprecedented nitrogen‐containing polycyclic aromatic hydrocarbons via mechanochemically assisted multifold reductive cyclodehydrogenation.
Simple, inexpensive, and robust cobalt‐based systems catalyze the 2+2+2 cycloaddition between unactivated nitriles and diarylacetylenes, including aryl and alkyl nitriles and cyanamides as well as di(hetero)arylacetylenes. The resulting tetra‐ and pentaarylpyridines undergo mechanochemistry‐enabled multifold cyclodehydrogenation to furnish nitrogen‐containing polycyclic aromatic compounds with unprecedented skeletons.
OBJECTIVE:The efficacy of therapeutic vaccines against HIV-1 infection has been modest. New inerts to redirect responses to vulnerable sites are urgently needed to improve these results.
DESIGN:We ...performed the first-in-human clinical trial with naked mRNA (iHIVARNA) combining a dendritic cell activation strategy (TriMix:CD40L+CD70+caTLR4 RNA) with a novel HIV immunogen sequences (HTI immunogen).
METHODS:A dose escalation, phase I clinical trial was performed in 21 chronic HIV-1-infected patients under ART who received three intranodal doses of mRNA (weeks 0, 2 and 4) as followTriMix-100 g, TriMix-300 g, TriMix-300 g with HTI-300 g, TriMix-300 g with HTI-600 g, TriMix-300 g with HTI-900 g. Primary end-point was safety and secondary-exploratory end-points were immunogenicity, changes in viral reservoir and transcriptome.
RESULTS:Overall, the vaccine was secure and well tolerated. There were 31 grade 1/2 and 1 grade 3 adverse events, mostly unrelated to the vaccination. Patients who received the highest dose showed a moderate increase in T-cell responses spanning HTI sequence at week 8. In addition, the proportion of responders receiving any dose of HTI increased from 31% at w0 to 80% postvaccination. The intervention had no impact on caHIV-DNA levels, however, caHIV-RNA expression and usVL were transiently increased at weeks 5 and 6 in the highest dose of iHIVARNA, and these changes were positively correlated with HIV-1-specific-induced immune responses.
CONCLUSION:This phase I dose-escalating trial showed that iHIVARNA administration was safe and well tolerated, induced moderate HIV-specific T-cell responses and transiently increased different viral replication readouts. These data support further exploration of iHIVARNA in a phase II study.
CLINICALTRIALS.GOV IDENTIFIER:NCT02413645
Main group mechanochemistry Gečiauskaitė, Agota A; García, Felipe
Beilstein journal of organic chemistry,
10/2017, Letnik:
13, Številka:
1
Journal Article
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Over the past decade, mechanochemistry has emerged as a powerful methodology in the search for sustainable alternatives to conventional solvent-based synthetic routes. Mechanochemistry has already ...been successfully applied to the synthesis of active pharmaceutical ingredients (APIs), organic compounds, metal oxides, coordination compounds and organometallic complexes. In the main group arena, examples of synthetic mechanochemical methodologies, whilst still relatively sporadic, are on the rise. This short review provides an overview of recent advances and achievements in this area that further validate mechanochemistry as a credible alternative to solution-based methods for the synthesis of main group compounds and frameworks.
Abstract
Mucosal immune response in the upper respiratory tract is crucial for initial control of viral replication, clearance of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), and ...progression of coronavirus disease 2019 (COVID-19). We analyzed SARS-CoV-2 RNA load and expression of selected immune genes in the upper respiratory tract (nasopharynx) of 255 SARS-CoV-2–infected patients and evaluated their association with severe COVID-19. SARS-CoV-2 replication in nasopharyngeal mucosa induces expression of several innate immune genes. High SARS-CoV-2 viral load and low CCL5 expression levels were associated with intensive care unit admission or death, although CCL5 was the best predictor of COVID-19 severity.
Graphical Abstract
Graphical Abstract
Soluble secretory proteins with a signal peptide reach the extracellular space through the endoplasmic reticulum-Golgi conventional pathway. During translation, the signal peptide is recognised by ...the signal recognition particle and results in a co-translational translocation to the endoplasmic reticulum to continue the secretory pathway. However, soluble secretory proteins lacking a signal peptide are also abundant, and several unconventional (endoplasmic reticulum/Golgi independent) pathways have been proposed and some demonstrated. This work describes new features of the secretion signal called Nβ, originally identified in NaTrxh, a plant extracellular thioredoxin, that does not possess an orthodox signal peptide. We provide evidence that other proteins, including thioredoxins type
h
, with similar sequences are also signal peptide-lacking secretory proteins. To be a secretion signal, positions 5, 8 and 9 must contain neutral residues in plant proteins–a negative residue in position 8 is suggested in animal proteins–to maintain the Nβ motif negatively charged and a hydrophilic profile. Moreover, our results suggest that the NaTrxh translocation to the endoplasmic reticulum occurs as a post-translational event. Finally, the Nβ motif sequence at the N- or C-terminus could be a feature that may help to predict protein localisation, mainly in plant and animal proteins.
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