Crystal structure and high-pressure properties of γ-Mo2N determined by neutron powder diffraction and X-ray diffraction

We prepared samples of cubic γ-MoN_x (x∼0.5) by high-pressure-high-temperature synthesis. N atom site occupancies within the defect rock salt structure were determined from time-of-flight neutron diffraction and powder X-ray diffraction data by Rietveld analysis. The results show that N atoms occupy only octahedral sites within the structure. The semi-metallic compound is a superconductor, with determined by SQUID magnetometry. The compressibility of the material was determined by synchrotron X-ray diffraction measurements at high pressure in the diamond anvil cell. The vibrational density of states was studied by Raman scattering spectroscopy.     

AFM studies of metal deposition: instantaneous nucleation and the growth of cobalt nanoparticles on boron-doped diamond electrodes.

In situ atomic force microscopy (AFM) is used to study the growth of cobalt nuclei on a boron doped diamond electrode under potentiostatic control. The rate of growth of the nuclei at the electrode surface is monitored using AFM as a function of time at different deposition potentials. The nucleation of cobalt nuclei is found to be "instantaneous" and the growth of the nuclei is shown to be kinetically rather than diffusionally controlled over periods of tens and hundreds of seconds. At very short times (<10 seconds) the kinetics of nucleation are apparent.     

Dense layers of vertically oriented WO3 crystals as anodes for photoelectrochemical water oxidation

Films of crystalline WO(3) nanosheets oriented perpendicular to tungsten substrates were grown by a surfactant-free hydrothermal method, followed by sintering. The films exhibit photoelectrochemical oxygen evolution at low overpotential.     

Reaction of carbonyl fluoride with fluorine in the presence of various fluorides as catalysts

The fluorides KF, RbF and CsF have been known to serve as catalysts for the reaction CF₂O + F₂→ CF₃OF. The list of catalysts for this process has now been enlarged to include NaF, MgF₂, CaF₂, SrF₂, BaF₂ and LaF₃. Lithium fluoride and thorium fluoride also give CF₃OF but are less active. Perhaps the substances CsF·HF, KAgF₄ and NiF₂ should be included in this list. Silver fluoride, usually as a mixture of AgF₂ with AgF, has been known to catalyze the reaction of CF₂O with F₂ to give both CF₃OF and CF₃OOCF₃. The proportion of the latter in the mixture of products increases with decreasing temperature. At 25°, the reaction is slow and the yield of CF₃OOCF₃ is very high. It has now been shown that TIF₃ behaves like silver fluoride. It has also been shown that many other fluorides of metals give higher yields of CF₃OOCF₃ than of CF₃OF but require higher temperatures than AgF₂ (100-ca. 150°) to be effective. Various possible mechanisms for these catalytic processes are discussed.     

Synthesis of a transition metal-dithionite complex, (η5-C5H5)(CO)2FeS(O)2S(O)2Fe(CO)2(η5-C5H5)

The reaction of Na[η⁵-C₅H₅Fe(CO)₂] with large excess of SO₂ in THF at ?78°C followed by warming to room temperature affords an iron—dithionite complex, (η⁵-C₅H₅)(CO)₂FeS(O)₂S(O)₂Fe(CO)₂(η⁵-C₅H₅).     

Pseudopolymorphic Clathrate Structures Formed by an Alicyclic Dialcohol Inclusion Host

Dialcohol host 2,7-dimethyltricyclo[4.3.1.0^3,8]undecane-syn-2,syn-7-diol 1 can form either ellipsoidal clathrate or helical tubulate inclusion compounds where only dispersion forces operate between the hosts and guests. The former (tetragonal space group I4₁/acd), built from two interpenetrating sublattices containing both diol enantiomers, encloses the guests in rugby ball-shaped cavities. The latter (trigonal space group P3₁21 or P3₂21), containing only one diol enantiomer, traps the guests within parallel tubes. Which inclusion type is produced is determined by the guest size and shape and, hence, control is possible over these structures. At room temperature, cyclohexane gives the tetragonal structure, but fluorocyclohexane yields the trigonal structure. Chloroform produces both pseudopolymorphs: the tetragonal form at higher and the trigonal form at lower temperatures. Powder and single-crystal structural X-ray data are reported for these clathrate compounds.     

Ruthenium‐Containing Linear Helicates and Mesocates with Tuneable p53‐Selective Cytotoxicity in Colorectal Cancer Cells

The ligands L¹ and L² both form separable dinuclear double‐stranded helicate and mesocate complexes with Ru^II. In contrast to clinically approved platinates, the helicate isomer of [Ru₂( L¹ )₂]⁴⁺ was preferentially cytotoxic to isogenic cells (HCT116 p53^?/?), which lack the critical tumour suppressor gene. The mesocate isomer shows the reverse selectivity, with the achiral isomer being preferentially cytotoxic towards HCT116 p53^+/+. Other structurally similar Ru^II‐containing dinuclear complexes showed very little cytotoxic activity. This study demonstrates that alterations in ligand or isomer can have profound effects on cytotoxicity towards cancer cells of different p53 status and suggests that selectivity can be “tuned” to either genotype. In the search for compounds that can target difficult‐to‐treat tumours that lack the p53 tumour suppressor gene, [Ru₂( L¹ )₂]⁴⁺ is a promising compound for further development.