Ferrocenyltrithiocarbonates : I. Direct access from α-ferrocenylcarbinols by a SNi mechanism. Absolute x-ray structure determination of (R)-ferrocenylmethylmethane S-methyl-trithiocarbonate

¹⁰³Rh Chemical shifts of a variety of mono- and di-nuclear rhodium carbonyl complexes are reported together with the modifications to the probe and decoupler unit of a JEOL PS-100 PFT spectrometer which enable these ¹⁰³Rh-decoupled ¹³C NMR measurements to be made. These data are discussed in conjunction with ¹³C NMR data on other rhodium carbonyls.     

α-Diimines as monodentate or bridging ligands; synthesis and characterization of palladium(II) and rhodium(I) di(t-butyl)diimine complexes

Complexes of di(t-butyl)diimine with PdCl₂(PhCN)₂ and with (CO)₂RhCl dimer have been synthesized and characterized. The diimine ligand is monodentate bonded in PdCl₂(t-butyldiimine)₂, while in (t-butyldiimine)-[Rh(CO)₂Cl]₂ it bridges two Cl(CO)₂Rh units.     

Arylmercury(II) compounds involving intramolecular coordination via 2-Me2NCH2- and chiral (S)-2-Me2NCHMe-ring substituents

Arylmercury compounds of the type Ar₂Hg and ArHgX (X = Cl, OAc) have been synthesized and characterized by ¹H and ¹³C NMR spectroscopy; the Ar group was either 2-Me₂NCH₂C₆H₄ or (S)-2-Me₂NCH(Me)C₆H₄, both of which contain N-donor ligands. The observation of anisochronous NMe resonances in (S)-2-Me₂NCH(Me)C₆H₄HgX (X = Cl, OAc) at low temperature indicates that in solution the mercury centre is three-coordinate as a result of stable intramolecular HgN coordination     

Effect of annealing on an amorphous GexTe1−x matrix with Te cristallites

Annealing shows very different behaviour for Te crystallites in an amorphous Ge_xTe_1?x matrix as a function of x (x = 0.1 … 0.5). For x ? 0.2, annealing at increasing temperatures increases the number (size) of the Te crystallites with subsequent GeTe + Te crystallization. However for x ? 0.3 there is first a disappearance of Te crystallites, then an appearance of GeTe crystallites, and subsequently GeTe + Te crystallization. Crystallites of either Te or GeTe act as extrinsic defects which add to the intrinsic ones. Activatioon energy decreases (increases) and conductance increases (decreases) as the number of defects increases (decreases). In all cases the final metallic state is obtained only when both GeTe and Te crystallites are present.     

Cancer-Associated Mutations of the Adenosine A2A Receptor Have Diverse Influences on Ligand Binding and Receptor Functions

The adenosine A_2A receptor (A_2AAR) is a class A G-protein-coupled receptor (GPCR). It is an immune checkpoint in the tumor micro-environment and has become an emerging target for cancer treatment. In this study, we aimed to explore the effects of cancer-patient-derived A_2AAR mutations on ligand binding and receptor functions. The wild-type A_2AAR and 15 mutants identified by Genomic Data Commons (GDC) in human cancers were expressed in HEK293T cells. Firstly, we found that the binding affinity for agonist NECA was decreased in six mutants but increased for the V275A mutant. Mutations A165V and A265V decreased the binding affinity for antagonist ZM241385. Secondly, we found that the potency of NECA (EC₅₀) in an impedance-based cell-morphology assay was mostly correlated with the binding affinity for the different mutants. Moreover, S132L and H278N were found to shift the A_2AAR towards the inactive state. Importantly, we found that ZM241385 could not inhibit the activation of V275A and P285L stimulated by NECA. Taken together, the cancer-associated mutations of A_2AAR modulated ligand binding and receptor functions. This study provides fundamental insights into the structure–activity relationship of the A_2AAR and provides insights for A_2AAR-related personalized treatment in cancer.     

Microporated PEG Spheres for Fluorescent Analyte Detection

Poly(ethylene glycol) (PEG) hydrogels have been used to encapsulate fluorescently labeled molecules in order to detect a variety of analytes. The hydrogels are designed with a mesh size that will retain the sensing elements while allowing for efficient diffusion of small analytes. Some sensing assays, however, require a conformational change or binding of large macromolecules, which may be sterically prohibited in a dense polymer matrix. A process of hydrogel microporation has been developed to create cavities within PEG microspheres to contain the assay components in solution. This arrangement provides improved motility for large sensing elements, while limiting leaching and increasing sensor lifetime. Three hydrogel compositions, 100% PEG, 50% PEG, and microporated 100% PEG, were used to create pH-sensitive microspheres that were tested for response time and stability. In order to assess motility, a second, more complex sensor, namely a FITC-dextran/TRITC-Con A glucose-specific assay was encapsulated within the microspheres.     

Enhanced Thermal Oxidation Stability of Reduced Graphene Oxide by Nitrogen Doping

Nitrogen‐doped reduced graphene oxide (N‐doped RGO) samples with a high level of doping, up to 13 wt. %, have been prepared by annealing graphene oxide under a flow of pure ammonia. The presence of nitrogen within the structure of RGO induces a remarkable increase in the thermal stability against oxidation by air. The thermal stability is closely related with the temperature of synthesis and the nitrogen content. The combustion reaction of nitrogen in different coordination environments (pyridinic, pyrrolic, and graphitic) is analyzed against a graphene fragment (undoped) from a thermodynamic point of view. In agreement with the experimental observations, the combustion of undoped graphene turns out to be more spontaneous than when nitrogen atoms are present.     

Slow turning reveals enormous quadrupolar interactions (STREAQI)

We introduce a new solid-state NMR method, which uses very slow sample rotation to visualize NMR spectra whose width exceeds feasible spectrometer bandwidths. It is based on the idea that if we reorient a tensor by a known angle about a known axis, the shifts in the NMR frequencies observed across the spectral width allow us to reconstruct the entire tensor. Called STREAQI (Slow Turning Reveals Enormous Anisotropic Quadrupolar Interactions), this method allows us to probe NMR nuclei that are intractable to current methods. To prove the concept and demonstrate its promise we have implemented the method for several 79Br containing samples with quadrupolar coupling constants in the range of 10-50 MHz.     

Set to set broadcasting in communication networks

Suppose G = (V,E) is a graph whose vertices represent people and edges represent telephone lines between pairs of people. Each person knows a unique message and is ignorant of the messages of other people at the beginning. These messages are then spread by telephone calls. In each call, two people exchange all information they have so far in exactly one unit of time. Suppose A and B are two nonempty subsets of V. The main purpose of this paper is to study the minimum number b(A,B,G) of telephone calls by which A broadcasts to B; and the minimum time t(A,B,G) such that A broadcasts to B. In particular, we give an exact formula for b(A,B,K_n) and linear-time algorithms for computing b(A,B,T) and t(A,B,T) of a tree T.     

The effect of spherical shells of matter on the Schwarzschild black hole

Based on previous work we show how to join two Schwarzschild solutions, possibly with different masses, along null cylinders each representing a spherical shell of infalling or outgoing massless matter. One of the Schwarzschild masses can be zero, i.e. one region can be flat. The above procedure can be repeated to produce space-times with aC ⁰ metric describing several different (possibly flat) Schwarzschild regions separated by shells of matter. An exhaustive treatment of the ways of combining four such regions is given; the extension to many regions is then straightforward. Cases of special interest are: (1) the scattering of two spherical gravitational shock waves at the horizon of a Schwarzschild black hole, and (2) a configuration involving onlyone external universe, which may be relevant to quantization problems in general relativity. In the latter example, only an infinitesimal amount of matter is sufficient to remove the Wheeler wormhole to another universe.Supported in part by the Stichting voor Fundamenteel Onderzoek der Materie