• Esbensen High opublikował 1 rok, 3 miesiące temu

    A red-light-mediated nPr-DMQA+-catalyzed cascade intramolecular trifluoromethylation and dearomatization of indole derivatives with Umemoto’s reagent has been developed. This protocol provides a facile and efficient approach for the construction of functionalized and potentially biologically important CF3-containing 3,3-spirocyclic indolines with moderate to high yields and excellent diastereoselectivities under mild conditions. The success of multiple gram-scale (1 and 10 g) experiments further highlights the robustness and practicality of this protocol and the merit of the employment of red light. Mechanistic studies support the formation of a crucial CF3 radical species and a dearomatized benzyl carbocation intermediate.Tropomyosin is a major allergen responsible for cross-allergenicity in a number of shellfish species. Although extensively characterized in marine crustaceans, the information of tropomyosin is limited to a few freshwater crustacean species. As a result, more cross-reactivity evidence and information of tropomyosin at the molecular level are required for the detection of freshwater crustaceans in the food industry. In this study, we explored tropomyosin allergenicity in four freshwater crustacean species prawn (Macrobrachium rosenbergii and Macrobrachium lanchesteri) and crayfish (Procambarus clarkii and Cherax quadricarinatus). Immunoblotting, liquid chromatography-tandem mass spectrometry, and immunoprecipitation studies indicated that tropomyosin was recognized by the sera’s IgE of crustacean-allergic volunteers. Cloning and characterization of nucleotide sequences of tropomyosin cDNA from M. lanchesteri and C. quadricarinatus revealed highly conserved amino acid sequences with other crustaceans. This study emphasized the role of tropomyosin as a universal marker for the detection of both freshwater and marine crustaceans in the food industry.Filamentous cyanobacteria are an essential element of oxygenic photogranules for granule-based wastewater treatment with photosynthetic aeration. Currently, mechanisms for the selection of this microbial group and their development in the granular structure are not well understood. Here, we studied the characteristics and fate of iron in photogranulation that proceeds in a hydrostatic environment with an activated sludge (AS) inoculum. We found that the level of Fe in bulk liquids (FeBL) sharply increased due to the decay of the inoculum but quickly diminished along with the bloom of microalgae and the advent of the oxic environment. Iron linked with extracellular polymeric substances (FeEPS) continued to decline but reached steady low values, which occurred along with the appearance of granular structure. Strong negative correlations were found between FeEPS and the pigments specific for cyanobacteria. Spectroscopies revealed the presence of amorphous ferric oxides in pellet biomass, which seemed to remain unaltered during the photogranulation process. These results suggest that the availability of FeEPS in AS inoculums-after algal bloom-selects cyanobacteria, and the limitation of this Fe pool becomes an important driver for cyanobacteria to granulate in a hydrostatic environment. We therefore propose that the availability of iron has a strong influence on the photogranulation process.Successful development of targeted therapeutics aimed at the elimination of diseased cells relies on the target properties and the therapeutics that target them. Currently, target properties have been evaluated through antibody-dependent semiquantitative approaches such as flow cytometry, Western blotting, or microscopy. Since antibodies can alter target properties following binding, antibody-dependent approaches provide at best skewed measurements for target intrinsic properties. To circumvent, here we attempted to develop an antibody-free targeted mass spectrometry-based (ATM) strategy to measure the surface densities and the intrinsic rates (Kint) of CD38 internalization in multiple myeloma cell lines. Using cell-surface biotinylation in conjunction with differential mass tagging to separate inward CD38 molecules from the outbound and nascent ones, the ATM approach revealed diversities in measured CD38 Kint values of 0.239 min-1 S.E. ± 0.076, 0.109 min-1 S.E. ± 0.032, and 0.058 min-1 S.E. ± 0.001 for LP1, NCIH929, and MOLP8 cell lines, respectively. Together with CD38 surface densities, intrinsic Kint values aligned well with the tumor penetration model and supported the outcomes for tumor regression in mouse xenografts upon drug treatment. Additionally, the ATM approach can evaluate molecules with fast Kint as we determined for CTLA4 protein. We believe that the ATM approach has the potential to evaluate diverse cell-surface targets as part of the pharmacological assessment in drug discovery.All-solid-state polymer electrolytes can improve the safety of lithium batteries. However, the common Bellcore polymer electrolyte technology faces several issues such as wasting a mass of solvent, high manufacturing cost, and poor interfacial compatibility between polymer electrolytes and electrodes. Herein, we propose an in situ polymerization technique to synthesize all-solid-state polymer electrolytes by a thiol-Michael addition click reaction. The alternating copolymer is made from the Michael addition reaction of ethylene glycol dimethacrylate (EGDMA) and 1,2-ethane dithiol (EDT). At ambient temperature, the obtained composite polymer electrolyte displays an ionic conductivity of 3.02 × 10-5 S/cm, an electrochemical window of 4.5 V, and a lithium-ion transference number of 0.45. In light of this unique polymerization process, the traditional fabrication method of liquid electrolyte-based lithium batteries can be adopted in the current study for the preparation of all-solid-state Li/LiFePO4 batteries. It was found that the assembled all-solid-state Li/LiFePO4 batteries exhibited superior charging/discharging performance and preferable safety. Thus, this facile and powerful in situ polymerization strategy may open up a new approach for the design and fabrication of all-solid-state batteries with desirable performances.While the phase separation of binary mixtures of chemically different polymer-grafted nanoparticles (PGNPs) is observed to superficially resemble conventional polymer blends, the presence of a „soft” polymer-grafted layer on the inorganic core of these nanoparticles qualitatively alters the phase separation kinetics of these „nanoblends” from the typical pattern of behavior seen in polymer blends and other simple fluids. We investigate this system using a direct immersion annealing method (DIA) that allows for a facile tuning of the PGNPs phase boundary, phase separation kinetics, and the ultimate scale of phase separation after a sufficient „aging” time. In particular, by switching the DIA solvent composition from a selective one (which increases the interaction parameter according to Timmerman’s rule) to an overall good solvent for both PGNP components, we can achieve rapid switchability between phase-separated and homogeneous states. Despite a relatively low and non-classical power-law coarsening exponent, the overall phase separation process is completed on a time scale on the order of a few minutes. Moreover, the roughness of the PGNP blend film saturates at a scale that is proportional to the in-plane phase separation pattern scale, as observed in previous blend and block copolymer film studies. The relatively low magnitude of the coarsening exponent n is attributed to a suppression of hydrodynamic interactions between the PGNPs. The DIA method provides a significant opportunity to control the phase separation morphology of PGNP blends by solution processing, and this method is expected to be quite useful in creating advanced materials.Aristolochic acid nephropathy (AAN) is a unique type of progressive renal interstitial fibrotic disease caused by prolonged exposure to aristolochic acids (AAs) through AA-containing herbal medicines or AA-tainted food. Despite decades of research and affecting millions of people around the world, the pathophysiology of AAN remains incompletely understood. In this study, we tested the potential causative role of mitochondrial dysfunction in AAN development. Our findings revealed AA exposure induces an exposure concentration and duration dependent lowering of adenosine triphosphate in both cultured human kidney and liver cells, highlighting an AA exposure effect on mitochondrial energy production in the kidney and liver, which both are highly metabolically active and energy-demanding organs. Analysis with liquid chromatography-tandem mass spectrometry coupled with stable isotope dilution method detected high levels of mutagenic 8-oxo-2′-deoxyguanosine and 7-(deoxyadenosine-N6-yl)-aristolactam adduct on mitochondrial DNA isolated from AA-treated cells, unmasking a potentially important causative, but previously unknown role of mitochondrial DNA mutation in the pathophysiology of AAN development.Herein, SnTe nanobelts (NBs) with efficient oxidase-mimetic activity were synthesized by the simple electrochemical exfoliation method. A specific inhibition effect of Cl- on the enzymatic behavior of the pure SnTe NBs was discovered, which was accordingly used for establishing a highly feasible, sensitive, selective, and stable Cl- colorimetric assay. The detection concentration range was 50 nM to 1 mM, and the lowest detection limit was 20 nM for Cl-. In addition, a signal on-off-on route based on the SnTe NB nanozyme was designed to realize the reliable and specific detection of Hg2+. Therein, the SnTe NBs were grafted with gold nanoparticles to form a hybrid of SnTe/Au, resulting in the depression of the oxidase-like activity, which can then be recovered in the presence of the Hg2+ due to the formation of a gold amalgam. Especially, it was found that the high concentration of Cl- over 3 mM could again exert suppression influence toward the enzymatic activity of the SnTe/Au-Hg system. Based on the to-love-and-to-kill interaction between Cl- and Hg2+, the detection range for Cl- can be extended to 40 to 250 mM. In return, the assays of Cl- could avoid in advance its interference toward the accurate Hg2+ assays. We systematically clarified the oxidase-like catalytic mechanism of the SnTe-derived nanozyme systems. The as-proposed colorimetry can be successfully applied in practical samples including the sweat, human serum, or seawater/tap water, relating to cystic fibrosis, hyper-/hypochloremia, or environmental control, respectively.Glyphosate (GLY) is a broad-spectrum herbicide and is the most used pesticide worldwide. This vast usage has raised strong interest in the ecotoxicological impacts and human risks, with contamination of water being a major concern. Decentralized analytical techniques for water monitoring are of high importance. In this work, we present a small, low-cost, and time-effective electrochemical, chip-based microfluidic device for direct electrochemical detection of GLY downstream of a molecularly imprinted polymer (MIP) concentrator. We studied the electrochemical behavior of GLY and its metabolite aminomethylphosphonic acid (AMPA) using cyclic voltammetry with noble metal electrodes in acidic, neutral, and basic media. A chronoamperometric sensor protocol was developed for sensitive and selective GLY measurements on gold electrodes. The optimized protocol was transferred to a chip-based microsensor platform for online and real-time detection of GLY in a microfluidic setup. The results in the range from 0 to 50 μM GLY in 0.

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