• Lykke Preston opublikował 5 miesięcy, 1 tydzień temu

    Imidazolium based receptors selectively recognize anions, and have received more and more attention. In 2006 and 2010, we reviewed the mechanism and progress of imidazolium salt recognition of anions, respectively. In the past ten years, new developments have emerged in this area, including some new imidazolium motifs and the identification of a wider variety of biological anions. In this review, we discuss the progress of imidazolium receptors for the recognition of anions in the period of 2010-2019 and highlight the trends in this area. We first classify receptors based on motifs, including some newly emerging receptors, as well as new advances in existing receptor types at this stage. Then we discuss separately according to the types of anions, including ATP, GTP, DNA and RNA.As coarse-grained (CG) studies of large biomolecules increase, developments of reliable CG solvent models become particularly important. In this work, we reduce five water molecules into a three-point CG model with permanent dipole and quadrupole moments. In the CG force field, the modified Morse potential is utilized and an ideal three-water cluster is designed to derive CG-level permanent multipoles. The new CG model is parametrized on the AMOEBA polarizable force field. Various important properties of liquid water are examined to validate the new CG model. Results show that the new CG model can correctly reproduce certain important experimental properties such as density, isothermal compressibility and relative static dielectric permittivity, even better than the existing AA models. Additionally, the CPU tests reveal that the CG model can accelerate molecular dynamics simulations by a factor of 19 compared to the popular AA force field. Compared with the fix-point-charge model widely used in other CG models, the permanent-multipole-based CG model describes more rigid electrostatic attractions. This study also illustrates that the permanent multipole moments contribute a lot to the electrostatic calculations in CG simulation.A zinc bromide-catalyzed synthesis of 5-substituted tetrazoles via DNA-conjugated nitriles using sodium azide has been developed. The protocol offered moderate to excellent yields of tetrazoles with a broad range of substrates, including a variety of functionalized aromatic, heterocyclic, and aliphatic nitriles. In addition, the electronic effect within the substrate scope was evaluated. DNA fidelity was assessed by ligation efficiency and amplifiability analysis. The ability to generate tetrazoles expands the diversity of heterocycles in the preparation of DNA-encoded chemical libraries.Circulating tumor cell (CTC) detection and enumeration have been considered as a noninvasive biopsy method for the diagnosis, characterization, and monitoring of various types of cancers. However, CTCs are exceptionally rare, which makes CTC detection technologically challenging. In the past few decades, much effort has been focused on highly efficient CTC capture, while the activity of CTCs has often been ignored. Here, we develop an effective method for nondestructive CTC capture, release, and detection. Folic acid (FA), as a targeting molecule, is conjugated on magnetic nanospheres through a cleavable disulfide bond-containing linker (cystamine) and a polyethylene glycol (PEG2k) linker, forming MN@Cys@PEG2k-FA nanoprobes, which can bind with folate receptor (FR) positive CTCs specifically and efficiently, leading to the capture of CTCs with an external magnetic field. When approximately 150 and 10 model CTCs were spiked in 1 mL of lysis blood, 93.1 ± 2.9% and 80.0 ± 9.7% CTCs were recovered, respectively. In total, 81.3 ± 2.6% captured CTCs can be released from MN@Cys@PEG2k-FA magnetic nanospheres by treatment with dithiothreitol. The released CTCs are easily identified from blood cells for specific detection and enumeration combined with immunofluorescence staining with a limit of detection of 10 CTC mL-1 lysed blood. Moreover, the released cells remain healthy with high viability (98.6 ± 0.78%) and can be cultured in vitro without detectable changes in morphology or behavior compared with healthy untreated cells. The high viability of the released CTCs may provide the possibility for downstream proteomics research of CTCs; therefore, cultured CTCs were collected for proteomics. As a result, 3504 proteins were identified. In conclusion, the MN@Cys@PEG2k-FA magnetic nanospheres prepared in this study may be a promising tool for early-stage cancer diagnosis and provide the possibility for downstream analysis of CTCs.Through use of a bespoke macrocyclic variant, we demonstrate a novel approach for tuning the reactivity of rhodium PNP pincer complexes that enables formation of conjugated enynes from terminal alkynes, rather than vinylidene derivates. This concept is illustrated using tert-butylacetylene as the substrate and rationalised by a ring-induced switch in mechanism.Elementary atomic mechanisms underlying nanoparticle growth in liquids are largely unexplored and mostly a subject of conjectures based on theory and indirect experimental insights. Direct, experimental observation of such processes at an atomic level requires imaging with single-atom sensitivity and control over kinetics. Although conventional liquid-cell (scanning) transmission electron microscopy ((S)TEM) enables nanoscale studies of dynamic processes, the visualization of atomic processes in the liquid phase is inhibited owing to the liquid film thickness and its encapsulation, both limiting the achievable spatial resolution. In contrast, by using thin, free-standing ionic liquid nanoreactors, this work shows that the mechanisms controlling and triggering particle growth can be uncovered at an atom-by-atom level. Our observations of growing particle ensembles reveal that diverse growth pathways proceed simultaneously. We record Ostwald ripening and oriented particle coalescence tracked at the atomic scale, which confirm the mechanisms suggested by theory. However, we also identify unexpected growth phenomena and more intricate coalescence events which show competing mechanisms. The diversity of the observed growth processes thus illustrates that growth reactions in liquids, on the atomic scale, are much more complex than predicted by theory. Furthermore, this work demonstrates that free-standing ionic liquids enable (sub-)Ångström resolution imaging of dynamic processes in liquids with single-atom sensitivity, thus providing a powerful alternative approach to conventional liquid-cell (S)TEM.Metal halide perovskites are semiconductors with many fascinating characteristics and their widespread use in optoelectronic devices has been expected. High-quality thin films and single crystals can be fabricated by simple chemical solution processes and their fundamental electrical, optical, and thermal properties can be changed significantly by compositional substitution, in particular halogen ions. In this perspective, we provide an overview of phonon and thermal properties of metal halide perovskites, which play a decisive role in determining device performance. After a brief introduction to fundamental material properties, longitudinal-optical phonons and unusual thermal properties of metal halide perovskites are discussed. Remarkably, they possess very low thermal conductivities and very large thermal expansion coefficients despite their crystalline nature. In line with these discussions, we present optical properties governed by the strong electron-phonon interactions and the unusual thermal properties. By showing their unique thermo-optic responses and novel application examples, we highlight some aspects of the unusual thermal properties.The aim of this study was to determine an in vitro evaluation method that could directly predict in vivo performance of decellularized tissue for cardiovascular use. We hypothesized that key factors for in vitro evaluation would be found by in vitro assessment of decellularized aortas that previously showed good performance in vivo, such as high patency. We chose porcine aortas, decellularized using three different decellularization methods sodium dodecyl-sulfate (SDS), freeze-thawing, and high-hydrostatic pressurization (HHP). Immunohistological staining, a blood clotting test, scanning electron microscopy (SEM) analysis, and recellularization of endothelial cells were used for the in vitro evaluation. There was a significant difference in the remaining extracellular matrix (ECM) components, ECM structure, and the luminal surface structure between the three decellularized aortas, respectively, resulting in differences in the recellularization of endothelial cells. On the other hand, there was no difference observed in the blood clotting test. These results suggested that the blood clotting test could be a key evaluation method for the prediction of in vivo performance. In addition, evaluation of the luminal surface structure and the recellularization experiment should be packaged as an in vitro evaluation because the long-term patency was probably affected. The evaluation approach in this study may be useful to establish regulations and a quality management system for a cardiovascular prosthesis.We demonstrate fine control of the nanocrystal size of ultrasmall Eu3+-doped Sc2O3 nanocrystals within an extremely small nanometer scale from 2.6 to 9.7 nm, thereby enabling us to thoroughly investigate the size-dependent surface-to-volume ratio in these ultrasmall NCs using an optical probe of the red-emitting Eu3+ ion for the first time.Exosomes (a type of nanoscale extracellular vesicle with a size range of 30-100 nm) mediate cell-cell communication by transferring functional biomolecules, and play an important role in various physiological and pathological processes, including tumor development and progression. More new and effective techniques for visualizing and tracking exosomes in cell-cell communication are highly desirable. However, the application of commonly used exosome-labeling probes is limited by the need for specificity and strict pH tolerance. We describe here the construction and testing of a novel exosome labeling fluorescent probe termed as „ExoTracker”, which displayed low cytotoxicity and a high fluorescence intensity in acidic environments. ExoTracker was applied for effective tracking of exosomes in cell endocytosis.A rarely porous Li-MOF (Li-AOIA) with surface area of 605 m2 g-1 was employed for the formation of an emerging class of solid-state lithium ion electrolytes. Infiltration of LiBF4 into Li-AOIA afforded Li-AOIA@BF4 with ionic conductivity of 1.09 × 10-5 S cm-1 at room temperature and an activation energy of 0.18 eV.Catalytically relevant intermediates in carbene transfer reactions from a diazo precursor were investigated using cobalt corrole complexes. Two divergent mechanisms are proposed depending on the oxidation state of the cobalt center. Mechanistically driven factors for the usage of cobalt corroles in carbene transfer reactions are discussed.A strategy of conformational tweaking regulates the condensed state behavior of naphthalimide skeletal isomers (NSIs) and enhances their photophysical properties, cellular uptake and prolonged imaging capability. This salient approach results in a large Stokes shift (>120 nm), rapid cellular internalization, photobleaching resistance, and efficient bioimaging of the ribbon-like nano-assembly superior to that of its electronically similar micro-flower isomer.

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