Cracking and the Indentation Size Effect for Knoop Hardness of Glasses

The Knoop hardnesses of five glasses decreased with increasing load in accordance with the classic indentation size effect (ISE). At moderate loads, cracking dramatically altered the indentation sizes and the ISE trends in three of the five glasses. Cracked indentations were as much as 10 μm longer than uncracked indentations made under identical conditions. Diagonal length readings must be corrected for optical resolution limitations if low power lenses are used.     

Edge Chipping Resistance of Alumina/Zirconia Laminates

The edge chipping test was used to measure the fracture resistance of alumina/alumina‐zirconia laminated structures. Tailored, symmetrical laminated structures were prepared with a variety of layer thickness. The laminates had a significantly greater edge chipping resistance. Laminates with thin layers were just as effective in impeding edge chips as laminates with thick layers.     

Polyethylene multiwalled carbon nanotube composites

Polyethylene (PE) multiwalled carbon nanotubes (MWCNTs) with weight fractions ranging from 0.1 to 10 wt% were prepared by melt blending using a mini-twin screw extruder. The morphology and degree of dispersion of the MWCNTs in the PE matrix at different length scales was investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and wide-angle X-ray diffraction (WAXD). Both individual and agglomerations of MWCNTs were evident. An up-shift of 17 cm⁻¹ for the G band and the evolution of a shoulder to this peak were obtained in the Raman spectra of the nanocomposites, probably due to compressive forces exerted on the MWCNTs by PE chains and indicating intercalation of PE into the MWCNT bundles. The electrical conductivity and linear viscoelastic behaviour of these nanocomposites were investigated. A percolation threshold of about 7.5 wt% was obtained and the electrical conductivity of PE was increased significantly, by 16 orders of magnitude, from 10⁻²⁰ to 10⁻⁴ S/cm. The storage modulus (G′) versus frequency curves approached a plateau above the percolation threshold with the formation of an interconnected nanotube structure, indicative of ‘pseudo-solid-like’ behaviour. The ultimate tensile strength and elongation at break of the nanocomposites decreased with addition of MWCNTs. The diminution of mechanical properties of the nanocomposites, though concomitant with a significant increase in electrical conductivity, implies the mechanism for mechanical reinforcement for PE/MWCNT composites is filler-matrix interfacial interactions and not filler percolation. The temperature of crystallisation (T_c) and fraction of PE that was crystalline (F_c) were modified by incorporating MWCNTs. The thermal decomposition temperature of PE was enhanced by 20 K on addition of 10 wt% MWCNT.     

Electron transfer/transport at metal-molecule interfaces probed by femtosecond time-resolved two-photon photoemission: Heptane and fullerene on Au(111)

Electron transfer and transport at metal-molecule interfaces has been a central problem in a number of disciplines. There is renewed interest in this problem from the rapidly growing field of molecule-based electronics, where the so-called “contact problem” is usually probed in transport measurements. Here, we probe interfacial electron transfer/transport using time-resolved two-photon photo-emission spectroscopy. Such an approach allows us to quantitatively measure the energetic alignment of occupied and unoccupied molecular orbitals to the metal Fermi level, the electronic coupling strength (or spectral density) between the molecular orbital and the metal substrate, and electronic-nuclear coupling leading to dynamic localization. These three types of information are in fact key ingredients in quantitative theories for electron transfer and transport at molecule-metal surfaces. Recent examples from our laboratory are used to illustrate the point. They include femtosecond dynamics of image potential resonances on heptane-covered Au(111) and exciton relaxation dynamics in C₆₀ epitaxial films on Au(111). On heptane/Au(111), the lifetime of the n = 1 image potential resonance increases from 52 fs at one monolayer (ML) coverage to 700 fs at 2 ML and 2.8 ps at 3 ML. On C₆₀/Au(111), the Frenkel exciton (involving the LUMO+1 level) couples over long distance to the metal substrate, with lifetime of 350 fs at 30 ML to 80 fs at 2 ML coverage. The film-thickness-dependent decay dynamics in both cases can be attributed to interfacial electron transfer. Fitting the distance-dependent electron transfer rates to a simple exponential function gives the characteristic distance parameter of ß = 0.6 ± 0.1 and 0.023 ± 0.005 Å⁻¹ for heptane- and C₆₀-covered Au(111), respectively. The difference in the ß parameters illustrates the essential role of the electronic structure of molecules in mediating interfacial electron transfer/transport.     

Isomeric Carborane Neuromuscular Blocking Agents

We synthesized a family of neuromuscular blocking agents (NMB) based on decamethonium, but containing a carborane cluster in the methylene chain between the two quaternary ammonium groups. The carborane cluster isomers o-NMB, m-NMB, and p-NMB were tested in animals for neuromuscular block and compared with agents used clinically: rocuronium and decamethonium. All three isomers caused reversible muscle weakness in mice as determined by grip strength and inverted screen tests, with a potency rank of p-NMB > rocuronium > decamethonium > m-NMB > o-NMB. The mechanism of action of the compounds was determined by using the in vitro rat phrenic nerve hemi-diaphragm preparation and electrophysiologic measurements in cells. Neostigmine reversed hemi-diaphragm weakness caused by the three isomers and rocuronium, but not succinylcholine. In electrophysiologic recordings of currents through acetylcholine receptor channels, the carborane compounds did not activate channel activity but did inhibit channel activation by acetylcholine. These results demonstrate that the carborane neuromuscular blocking agents are non-depolarizers in contrast to the depolarizing action of the parent compound.     

Native Mass Spectrometry for the Study of PROTAC GNE-987-Containing Ternary Complexes

PRO teolysis TA rgeting C himeras (PROTACs) promote the degradation, rather than inhibition, of a drug target as a mechanism for therapeutic treatment. Bifunctional PROTAC molecules allow simultaneous binding of both the target protein and an E3-Ubiquitin ligase, bringing the two proteins into close spatial proximity to allow ubiquitinylation and degradation of the target protein via the cell's endogenous protein degradation pathway. We utilized native mass spectrometry (MS) to study the ternary complexes promoted by the previously reported PROTAC GNE-987 between Brd4 bromodomains 1 and 2, and Von Hippel Lindeau E3-Ubiquitin Ligase. Native MS at high resolution allowed us to measure ternary complex formation as a function of PROTAC concentration to provide a measure of complex affinity and stability, whilst simultaneously measuring other intermediate protein species. Native MS provides a high-throughput, low sample consumption, direct screening method to measure ternary complexes for PROTAC development.