Rhodesbradley2990

The epitaxial growth of single-crystal thin films relies on the availability of a single-crystal substrate and a strong interaction between epilayer and substrate. Previous studies have reported the roles of the substrate (e.g., symmetry and lattice constant) in determining the orientations of chemical vapor deposition (CVD)-grown graphene, and Cu(111) is considered as the most promising substrate for epitaxial growth of graphene single crystals. However, the roles of gas-phase reactants and graphene-substrate interaction in determining the graphene orientation are still unclear. Here, we find that trace amounts of oxygen is capable of enhancing the interaction between graphene edges and Cu(111) substrate and, therefore, eliminating the misoriented graphene domains in the nucleation stage. A modified anomalous grain growth method is developed to improve the size of the as-obtained Cu(111) single crystal, relying on strongly textured polycrystalline Cu foils. The batch-to-batch production of A3-size (∼0.42 × 0.3 m2) single-crystal graphene films is achieved on Cu(111) foils relying on a self-designed pilot-scale CVD system. The as-grown graphene exhibits ultrahigh carrier mobilities of 68 000 cm2 V-1 s-1 at room temperature and 210 000 cm2 V-1 s-1 at 2.2 K. The findings and strategies provided in our work would accelerate the mass production of high-quality misorientation-free graphene films.The radionuclides 225Ac3+ and 213Bi3+ possess favorable physical properties for targeted alpha therapy (TAT), a therapeutic approach that leverages α radiation to treat cancers. A chelator that effectively binds and retains these radionuclides is required for this application. The development of ligands for this purpose, however, is challenging because the large ionic radii and charge-diffuse nature of these metal ions give rise to weaker metal-ligand interactions. In this study, we evaluated two 18-membered macrocyclic chelators, macrodipa and py-macrodipa, for their ability to complex 225Ac3+ and 213Bi3+. Their coordination chemistry with Ac3+ was probed computationally and with Bi3+ experimentally via NMR spectroscopy and X-ray crystallography. Furthermore, radiolabeling studies were conducted, revealing the efficient incorporation of both 225Ac3+ and 213Bi3+ by py-macrodipa that matches or surpasses the well-known chelators macropa and DOTA. Incubation in human serum at 37 °C showed that ∼90% of the 225Ac3+-py-macrodipa complex dissociates after 1 d. The Bi3+-py-macrodipa complex possesses remarkable kinetic inertness reflected by an EDTA transchelation challenge study, surpassing that of Bi3+-macropa. This work establishes py-macrodipa as a valuable candidate for 213Bi3+ TAT, providing further motivation for its implementation within new radiopharmaceutical agents.Empowered by crystalline ordered structures and homogeneous fabrication techniques, covalent organic frameworks (COFs) have been realized with uniform morphologies and isotropic properties. However, such homogeneity often hinders various surface-dependent properties observed in asymmetric nanostructures. The challenge remains to induce heterogeneity in COFs by creating an asymmetric superstructure such as a Janus thin film. In this regard, we propose a versatile yet straightforward interfacial layer-grafting strategy to fabricate free-standing Janus-type COF-graphene thin films. Herein, two-dimensional graphene sheets were utilized as the suitable grafter due to the possibility of noncovalent interactions between the layers. The versatility of the approach was demonstrated by fabricating two distinct Janus-type films, with the COF surface interwoven with nanofibers and nanospheres. The Janus-type films showcase opposing surface morphologies originating from graphene sheets and COF nanofibers or nanospheres, preserving the porosity (552-600 m2 g-1). The unique surface chemistries of the constituent layers further endow the films with orthogonal mechanical properties, as confirmed by the nanoindentation technique. Interestingly, the graphene sheets favor the Janus-type assembly of COF nanofibers over the nanospheres. This is reflected in the better nanomechanical properties of COFfiber-graphene films (Egraphene = 300-1200 MPa; ECOF = 15-60 MPa) compared to the COFsphere-graphene films (Egraphene = 11-14 MPa; ECOF = 2-5 MPa). These results indicate a direct relationship between the mechanical properties and homo/heterogeneity of Janus-type COF films.Ultraviolet (UV) laser photolysis of hydrogen peroxide (H2O2) for the in situ generation of hydroxyl radicals (•OH) is a widely utilized strategy in the oxidation footprinting of native proteins and mass spectrometry (MS)-based structural analysis. However, it remains challenging to realize peroxide-free photochemical oxidation footprinting. Herein, we describe the footprinting of native proteins by chloride-mediated peroxide-free photochemical oxidation of proteins (PPOP). The protein samples are prepared within biocompatible phosphate-buffered saline (PBS) containing 10 mM Gln as radical scavengers and oxidized in a capillary flow reactor directly under a single-pulse (10 ns) irradiation of a 193 nm ArF UV laser. The main oxidized protein residues are CMYWFHLI. We demonstrate that the PPOP-MS strategy is highly sensitive to the protein high-order structures and can be applied to monitor the protein-drug interfaces, which provides a promising footprinting alternative for protein structure-function explorations.Single-crystal X-ray diffraction studies of pristine and γ-irradiated Ca2[UO2(O2)3]·9H2O reveal site-specific atomic-scale changes during the solid-state progression from a crystalline to X-ray amorphous state with increasing dose. Following γ-irradiation to 1, 1.5, and 2 MGy, the peroxide group not bonded to Ca2+ is progressively replaced by two hydroxyl groups separated by 2.7 Å (with minor changes in the unit cell), whereas the peroxide groups bonded to Ca2+ cations are largely unaffected by irradiation prior to amorphization, which occurs by a dose of 3 MGy. The conversion of peroxide to hydroxyl occurs through interaction of neighboring lattice H2O molecules and ionization of the peroxide O-O bond, which produces two hydroxyls, and allows isolation of the important monomer building block, UO2(O2)2(OH)24-, that is ubiquitous in uranyl capsule polyoxometalates. Steric crowding in the equatorial plane of the uranyl ion develops and promotes transformation to an amorphous phase. In contrast, γ-irradiation of solid Li4[(UO2)(O2)3]·10H2O results in a solid-state transformation to a well-crystallized peroxide-free uranyl oxyhydrate containing sheets of equatorial edge and vertex-sharing uranyl pentagonal bipyramids with likely Li and H2O in interlayer positions. The irradiation products of these two uranyl triperoxide monomers are compared via X-ray diffraction (single-crystal and powder) and Raman spectroscopy, with a focus on the influence of the Li+ and Ca2+ countercations. Highly hydratable and mobile Li+ yields to uranyl hydrolysis reactions, while Ca2+ provides lattice rigidity, allowing observation of the first steps of radiation-promoted transformation of uranyl triperoxide.While the color of metallic gold is a prominent and well-investigated example for the impact of relativistic effects, much less is known regarding the influence on its melting and boiling point (MP/BP). To remedy this situation, this work takes on the challenging task of exploring the phase transitions of the Group 11 coinage metals Cu, Ag, and Au through nonrelativistic (NR) and scalar/spin-orbit relativistic (SR/SOR) Gibbs energy calculations with λ-scaled density-functional theory (λDFT). At the SOR level, the calculations provide BPs in excellent agreement with experimental values (1%), while MPs exhibit more significant deviations (2-10%). Comparing SOR calculations to those conducted in the NR limit reveals some remarkably large and, at the same time, some surprisingly small relativistic shifts. Most notably, the BP of Au increases by about 800 K due to relativity, which is in line with the strong relativistic increase of the cohesive energy, whereas the MP of Au is very similar at the SOR and NR levels, defying the typically robust correlation between MP and cohesive energy. Eventually, an inspection of thermodynamic quantities traces the trend-breaking behavior of Au back to phase-specific effects in liquid Au, which render NR Au more similar to SOR Ag, in line with a half-a-century-old hypothesis of Pyykkö.Glioblastoma multiforme (GBM) is the most aggressive brain tumor, characterized by short median survival and an almost 100% tumor-related mortality. The standard of care treatment for newly diagnosed GBM includes surgical resection followed by concomitant radiochemotherapy. The prevention of disease progression fails due to the poor therapeutic effect caused by the great molecular heterogeneity of this tumor. Previously, we exploited synchrotron radiation-based soft X-ray tomography and hard X-ray fluorescence for elemental microimaging of the shock-frozen GBM cells. The present study focuses instead on the biochemical profiling of live GBM cells and provides new insight into tumor heterogenicity. see more We studied bio-macromolecular changes by exploring the live-cell synchrotron-based Fourier transform infrared (SR-FTIR) microspectroscopy in a set of three GBM cell lines, including the patient-derived glioblastoma cell line, before and after riluzole treatment, a medicament with potential anticancer properties. SR-FTIR microspectroscopy shows that GBM live cells of different origins recruit different organic compounds. The riluzole treatment of all GBM cell lines mainly affected carbohydrate metabolism and the DNA structure. Lipid structures and protein secondary conformation are affected as well by the riluzole treatment cellular proteins assumed cross β-sheet conformation while parallel β-sheet conformation was less represented for all GBM cells. Moreover, we hope that a new live-cell approach for GBM simultaneous treatment and examination can be devised to target cancer cells more specifically, i.e., future therapies can develop more specific treatments according to the specific bio-macromolecular signature of each tumor type.Peracetic acid (PAA) is an emerging oxidant and disinfectant for wastewater (WW) treatment due to limited harmful disinfection byproduct (DBP) formation. Nitrite (NO2-) is a ubiquitous anion in water, but the impact of NO2- on PAA oxidation and disinfection has been largely overlooked. This work found for the first time that NO2- could significantly promote the oxidation of sulfonamide antibiotics (SAs) by PAA. Unexpectedly, the reactive nitrogen species (RNS), for example, peroxynitrite (ONOO-), rather than conventional organic radicals (R-O•) or reactive oxygen species (ROS), played major roles in SAs degradation. A kinetic model based on first-principles was developed to elucidate the reaction mechanism and simulate reaction kinetics of the PAA/NO2- process. Structural activity assessment and quantum chemical calculations showed that RNS tended to react with an aromatic amine group, resulting in more conversion of NO2--N to organic-N. The formation of nitrated and nitrosated byproducts and the enhancement of trichloronitromethane formation potential might be a prevalent problem in the PAA/NO2- process.