Huangkent9470

By developing an IMC marker for the detection of Salmonella LPS, we were further able to identify and characterize those cell types which contained S. Typhimurium.Control of single electron spins constitutes one of the most promising platforms for spintronics, quantum sensing, and quantum information processing. Utilizing single molecular magnets as their hosts establishes an interesting framework since their molecular structure is highly flexible and chemistry-based large-scale synthesis directly provides a way toward scalability. CDK inhibitor Here, we demonstrate coherent spin manipulation of single molecules on a surface, which we control individually using a scanning tunneling microscope in combination with electron spin resonance. We previously found that iron phthalocyanine (FePc) molecules form a spin-1/2 system when placed on an insulating thin film of magnesium oxide (MgO). Performing Rabi oscillation and Hahn echo measurements, we show that the FePc spin can be coherently manipulated with a phase coherence time T2Echo of several hundreds of nanoseconds. Tunneling current-dependent measurements demonstrate that interaction with the tunneling electrons is the dominating source of decoherence. In addition, we perform Hahn echo measurements on small self-assembled arrays of FePc molecules. We show that, despite additional intermolecular magnetic coupling, spin resonance and T2Echo are much less perturbed by T1 spin flip events of neighboring spins than by the tunneling current. This will potentially allow for individual addressable molecular spins in self-assemblies and with application for quantum information processing.Smart materials can respond to stimuli and adapt their responses based on external cues from their environments. Such behavior requires a way to transport energy efficiently and then convert it for use in applications such as actuation, sensing, or signaling. Ultrasound can carry energy safely and with low losses through complex and opaque media. It can be localized to small regions of space and couple to systems over a wide range of time scales. However, the same characteristics that allow ultrasound to propagate efficiently through materials make it difficult to convert acoustic energy into other useful forms. Recent work across diverse fields has begun to address this challenge, demonstrating ultrasonic effects that provide control over physical and chemical systems with surprisingly high specificity. Here, we review recent progress in ultrasound-matter interactions, focusing on effects that can be incorporated as components in smart materials. These techniques build on fundamental phenomena such as cavitation, microstreaming, scattering, and acoustic radiation forces to enable capabilities such as actuation, sensing, payload delivery, and the initiation of chemical or biological processes. The diversity of emerging techniques holds great promise for a wide range of smart capabilities supported by ultrasound and poses interesting questions for further investigations.Carbon monoxide (CO) is a well-known inhibitor of nitrogenase activity. Under turnover conditions, CO binds to FeMoco, the active site of Mo nitrogenase. Time-resolved IR measurements suggest an initial terminal CO at 1904 cm-1 that converts to a bridging CO at 1715 cm-1, and an X-ray structure shows that CO can displace one of the bridging belt sulfides of FeMoco. However, the CO-binding redox state(s) of FeMoco (En) and the role of the protein environment in stabilizing specific CO-bound intermediates remain elusive. In this work, we carry out an in-depth analysis of the CO-FeMoco interaction based on quantum chemical calculations addressing different aspects of the electronic structure. (1) The local electronic structure of the Fe-CO bond is studied through diamagnetically substituted FeMoco. (2) A cluster model of FeMoco within a polarizable continuum illustrates how CO binding may affect the spin-coupling between the metal centers. (3) A QM/MM model incorporates the explicit influence of the amino acid residues surrounding FeMoco in the MoFe protein. The QM/MM model predicts both a terminal and a bridging CO in the E1 redox state. The scaled calculated CO frequencies (1922 and 1716 cm-1, respectively) are in good agreement with the experimentally observed IR bands supporting CO binding to the E1 state. Alternatively, an E2 state QM/MM model, which has the same atomic structure as the CO-bound X-ray structure, features a semi-bridging CO with a scaled calculated frequency (1718 cm-1) similar to the bridging CO in the E1 model.Hookworm infections affect millions of people worldwide and are responsible for impaired mental and physical growth in children, and anemias. There is no vaccine, and increasing anthelmintic drug resistance in nematodes of domestic animals, and reduced drug cure rates in nematode infections of humans is alarming. Despite this looming health problem, there is a significant knowledge gap in terms of nonproteinaceous "excretory/secretory products" (ESPs) and how they orchestrate a parasitic existence. In the current study, we have conducted the first metabolomic and lipidomic analysis of the infective third-stage filariform larvae (L3) of the predominant human hookworm Necator americanus using liquid chromatography-mass spectrometry. Altogether, we have identified a total of 645 small molecules that were mainly produced through amino acid and glycerophospholipid metabolism. Putatively, 495 metabolites were unique to the somatic tissue extract, and 34 metabolites were present only in the ESP component. More than 21 novel mass features with nitrogen and sulfur functional groups were detected in the ESP component for the first time from helminths. While this study could not establish the biological functions of the metabolites identified, literature searches revealed that these metabolites possess various biological properties, including anti-inflammatory activities. These metabolites are likely used by the parasite upon exposure to a host to facilitate skin penetration, passage through different tissues, and immune regulation in the small bowel. Overall, the results presented herein offer significant insight into the metabolome of N. americanus L3 and have the potential to instigate future work to establish biomarkers of infection. This area urgently needs attention, given the lack of sensitive point-of-care diagnostic tools.G-protein-coupled receptors (GPCRs) are the molecular target of 40% of marketed drugs and the most investigated structures to develop novel therapeutics. Different members of the GPCRs superfamily can modulate the same cellular process acting on diverse pathways, thus representing an attractive opportunity to achieve multitarget drugs with synergic pharmacological effects. Here, we present a series of compounds with dual activity toward cysteinyl leukotriene receptor 1 (CysLT1R) and G-protein-coupled bile acid receptor 1 (GPBAR1). They are derivatives of REV5901─the first reported dual compound─with therapeutic potential in the treatment of colitis and other inflammatory processes. We report the binding mode of the most active compounds in the two GPCRs, revealing unprecedented structural basis for future drug design studies, including the presence of a polar group opportunely spaced from an aromatic ring in the ligand to interact with Arg792.60 of CysLT1R and achieve dual activity.The preparation of two new neptunium hydroxide compounds synthesized in concentrated potassium and rubidium hydroxide is reported. The phases K4[(NpO2)2(OH)6]·4H2O and Rb4[(NpO2)4(OH)8]·2H2O were prepared and their chemical structures determined using single-crystal X-ray diffraction. Raman spectra of the compounds are also presented. The newly synthesized phases are structurally related to Np2O5 and Na[NpO2(OH)2]. The potassium-containing phase reported here consists of infinite chains of edge-sharing neptunium hydroxide polyhedra but lacking the cation-cation interactions (CCIs) observed in Np2O5 and Na[NpO2(OH)2]. Rb4[(NpO2)4(OH)8]·2H2O is a an expanded three-dimensional framework based on NpO2+ CCIs like those observed in Np2O5 and Na[NpO2(OH)2]. Together these complexes begin to develop a structural series of neptunium(V) oxides and hydroxides of varying dimensionalities within the alkali-metal series. The potential roles of the alkali-metal cations and neptunyl(V) CCIs in directing the resulting structures are discussed.Bacteria proficient at producing cellulose are an attractive synthetic biology host for the emerging field of Engineered Living Materials (ELMs). Species from the Komagataeibacter genus produce high yields of pure cellulose materials in a short time with minimal resources, and pioneering work has shown that genetic engineering in these strains is possible and can be used to modify the material and its production. To accelerate synthetic biology progress in these bacteria, we introduce here the Komagataeibacter tool kit (KTK), a standardized modular cloning system based on Golden Gate DNA assembly that allows DNA parts to be combined to build complex multigene constructs expressed in bacteria from plasmids. Working in Komagataeibacter rhaeticus, we describe basic parts for this system, including promoters, fusion tags, and reporter proteins, before showcasing how the assembly system enables more complex designs. Specifically, we use KTK cloning to reformat the Escherichia coli curli amyloid fiber system for functional expression in K. rhaeticus, and go on to modify it as a system for programming protein secretion from the cellulose producing bacteria. With this toolkit, we aim to accelerate modular synthetic biology in these bacteria, and enable more rapid progress in the emerging ELMs community.Electrochemical reduction of CO2 on copper-based catalysts has become a promising strategy to mitigate greenhouse gas emissions and gain valuable chemicals and fuels. Unfortunately, however, the generally low product selectivity of the process decreases the industrial competitiveness compared to the established large-scale chemical processes. Here, we present random solid solution Cu1-xNix alloy catalysts that, due to their full miscibility, enable a systematic modulation of adsorption energies. In particular, we find that these catalysts lead to an increase of hydrogen evolution with the Ni content, which correlates with a significant increase of the selectivity for methane formation relative to C2 products such as ethylene and ethanol. From experimental and theoretical insights, we find the increased hydrogen atom coverage to facilitate Langmuir-Hinshelwood-like hydrogenation of surface intermediates, giving an impressive almost 2 orders of magnitude increase in the CH4 to C2H4 + C2H5OH selectivity on Cu0.87Ni0.13 at -300 mA cm-2. This study provides important insights and design concepts for the tunability of product selectivity for electrochemical CO2 reduction that will help to pave the way toward industrially competitive electrocatalyst materials.In this work, we have synthesized a series of novel C,N-cyclometalated 2H-indazole-ruthenium(II) and -iridium(III) complexes with varying substituents (H, CH3, isopropyl, and CF3) in the R4 position of the phenyl ring of the 2H-indazole chelating ligand. All of the complexes were characterized by 1H, 13C, high-resolution mass spectrometry, and elemental analysis. The methyl-substituted 2H-indazole-Ir(III) complex was further characterized by single-crystal X-ray analysis. The cytotoxic activity of new ruthenium(II) and iridium(III) compounds has been evaluated in a panel of triple negative breast cancer (TNBC) cell lines (MDA-MB-231 and MDA-MB-468) and colon cancer cell line HCT-116 to investigate their structure-activity relationships. Most of these new complexes have shown appreciable activity, comparable to or significantly better than that of cisplatin in TNBC cell lines. R4 substitution of the phenyl ring of the 2H-indazole ligand with methyl and isopropyl substituents showed increased potency in ruthenium(II) and iridium(III) complexes compared to that of their parent compounds in all cell lines.