Surface‐sampled simulations of turbulent flow at high Reynolds number

A new approach to turbulence simulation, based on a combination of large eddy simulation (LES) for the whole flow and an array of non–space‐filling quasi‐direct numerical simulations (QDNS), which sample the response of near‐wall turbulence to large‐scale forcing, is proposed and evaluated. The technique overcomes some of the cost limitations of turbulence simulation, since the main flow is treated with a coarse‐grid LES, with the equivalent of wall functions supplied by the near‐wall sampled QDNS. Two cases are tested, at friction Reynolds number Re_τ=4200 and 20000. The total grid point count for the first case is less than half a million and less than 2 million for the second case, with the calculations only requiring a desktop computer. A good agreement with published direct numerical simulation (DNS) is found at Re_τ=4200, both in the mean velocity profile and the streamwise velocity fluctuation statistics, which correctly show a substantial increase in near‐wall turbulence levels due to a modulation of near‐wall streaks by large‐scale structures. The trend continues at Re_τ=20000, in agreement with experiment, which represents one of the major achievements of the new approach. A number of detailed aspects of the model, including numerical resolution, LES‐QDNS coupling strategy and subgrid model are explored. A low level of grid sensitivity is demonstrated for both the QDNS and LES aspects. Since the method does not assume a law of the wall, it can in principle be applied to flows that are out of equilibrium.     

Encapsulation of Pt(iv) prodrugs within a Pt(ii) cage for drug delivery

This report presents a novel strategy that facilitates delivery of multiple, specific payloads of Pt(iv) prodrugs using a well-defined supramolecular system. This delivery system comprises a hexanuclear Pt(ii) cage that can host four Pt(iv) prodrug guest molecules. Relying on host–guest interactions between adamantyl units tethered to the Pt(iv) molecules and the cage, four prodrugs could be encapsulated within one cage. This host–guest complex, exhibiting a diameter of about 3 nm, has been characterized by detailed NMR spectroscopic measurements. Owing to the high positive charge, this nanostructure exhibits high cellular uptake. Upon entering cells and reacting with biological reductants such as ascorbic acid, the host–guest complex releases cisplatin, which leads to cell cycle arrest and apoptosis. The fully assembled complex displays cytotoxicity comparable to that of cisplatin against a panel of human cancer cell lines, whereas the cage or the Pt(iv) guest alone exhibit lower cytotoxicity. These findings indicate the potential of utilising well-defined supramolecular constructs for the delivery of prodrug molecules.     

Genomics-driven discovery of chiral triscatechol siderophores with enantiomeric Fe(iii) coordination

Ferric complexes of triscatechol siderophores may assume one of two enantiomeric configurations at the iron site. Chirality is known to be important in the iron uptake process, however an understanding of the molecular features directing stereospecific coordination remains ambiguous. Synthesis of the full suite of (DHB^L/DLys^L/DSer)₃ macrolactone diastereomers, which includes the siderophore cyclic trichrysobactin (CTC), enables the effects that the chirality of Lys and Ser residues exert on the configuration of the Fe(iii) complex to be defined. Computationally optimized geometries indicate that the Λ/Δ configurational preferences are set by steric interactions between the Lys sidechains and the peptide backbone. The ability of each (DHB^L/DLys^L/DSer)₃ diastereomer to form a stable Fe(iii) complex prompted a genomic search for biosynthetic gene clusters (BGCs) encoding the synthesis of these diastereomers in microbes. The genome of the plant pathogen Dickeya chrysanthemi EC16 was sequenced and the genes responsible for the biosynthesis of CTC were identified. A related but distinct BGC was identified in the genome of the opportunistic pathogen Yersinia frederiksenii ATCC 33641; isolation of the siderophore from Y. frederiksenii ATCC 33641, named frederiksenibactin (FSB), revealed the triscatechol oligoester, linear-(DHB^LLys^LSer)₃. Circular dichroism (CD) spectroscopy establishes that Fe(iii)–CTC and Fe(iii)–FSB are formed in opposite enantiomeric configuration, consistent with the results of the ferric complexes of the cyclic (DHB^L/DLys^L/DSer)₃ diastereomers.

Synthesis and genome mining leverage access to diastereomers of the siderophore cyclic trichrysobactin. Computational modeling and CD spectroscopy address effects that ligand-based stereochemistry exerts on the configuration at Fe(iii).     

Technetium tetrachloride revisited: a precursor to lower-valent binary technetium chlorides

Technetium tetrachloride has been prepared from the reaction of technetium metal with excess chlorine in sealed Pyrex ampules at elevated temperatures. The product was characterized by single-crystal and powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and alternating-current magnetic susceptibility. Solid TcCl(4) behaves as a simple paramagnet from room temperature down to 50 K with μ(eff) = 3.76 μ(B). Below 25 K, TcCl(4) exhibits an antiferromagnetic transition with a Néel temperature (T(N)) of ～24 K. The thermal behavior of TcCl(4) was investigated under vacuum at 450 °C; the compound decomposes stepwise to α-TcCl(3) and TcCl(2).     

Magnetic moment measurements in the semi-magic nuclei 94Ru and 95Rh after recoil implantation into iron and nickel

The magnetic moments of the 12⁺ and 11⁻ yrast states in ⁹⁴Ru and of the 25/2⁻, 29/2⁺, and 35/2⁺ levels in ⁹⁵Rh have been measured via the IMPAD technique. The nuclei were produced in the reaction ⁵⁸Ni +⁴⁰Ca and recoil-implanted into polarized Ni and Fe hosts. The g-factors were deduced from the measured time-integral Larmor precessions. The comparison between the experimental results and large-scale shell model calculations suggests that the 12⁺ and 11⁻ states in ⁹⁴Ru and the 25/2⁻ level in ⁹⁵Rh are pure proton states whereas the 29/2⁺ and 35/2⁺ states in ⁹⁵Rh contain a neutron excitation across the N=50 shell gap. This interpretation supports the conclusion drawn from recent lifetime measurements. Received: 2 June 1999     

Modular Synthesis of Linear Bis‐ and Tris‐monodentate Fused [6]Polynorbornane‐Based Ligands and their Assembly into Coordination Cages

A modular approach has been developed for the synthesis of rigid linear di‐ and tritopic ligands based on a fused [6]polynorbornane scaffold. The design provides up to three sites for installing functionality, including both “ends” and a “central” position with the advantage that each region can be independently addressed during synthesis. To illustrate the utility of the approach, both pyridyl and picolyl units were incorporated to provide six new ligands, with centers and ends either matched or mismatched. Indeed, both [M₂L₄] cages with endohedral functionality and [M₃L₄] complexes were cleanly produced from these ligands with assembled structures confirmed by using ¹H NMR spectroscopy, HRMS, and molecular modelling.