Ground state of magnetic dimers on metal surfaces

We present model studies of the ground state for magnetic dimers on metal surfaces. We find it can be neither ferromagnetic nor antiferromagnetic, but is often canted for nearest neighbors. Thus, the system cannot be described using bilinear exchange. We give a criterion which can be used quite generally to interrogate the local stability of ferromagnetically or antiferromagnetically aligned dimers, and which also may be used to infer the canting angle when canted states are stable.     

Strongly enhanced hole-phonon coupling in the metallic state of the dilute two-dimensional hole gas

We have studied the temperature dependent phonon emission rate P(T) of a strongly interacting (r(s) > or =22) dilute 2D GaAs hole system using a standard carrier heating technique. In the still poorly understood metallic state, we observe that P(T) changes from P(T) approximately T5 to P(T) approximately T7 above 100 mK, indicating a crossover from screened piezoelectric (PZ) coupling to screened deformation potential (DP) coupling for hole-phonon scattering. Quantitative comparison with theory shows that the long range PZ coupling between holes and phonons has the expected magnitude; however, in the metallic state, the short range DP coupling between holes and phonons is almost 20 times stronger than expected from theory. The density dependence of P(T) shows that it is easier to cool low-density 2D holes in GaAs than higher density 2D hole systems.     

3D ultrasound guided breast biopsy system

Stereotactic X-ray mammography (SM) and ultrasound (US) guidance are commonly used techniques for breast biopsy. While SM provides 3D targeting information and US provides real-time guidance, both techniques have limitations. SM is a long and uncomfortable procedure and the US guided procedure is inherently 2D, requiring a skilled physician for both safety and accuracy. We have developed a 3D US-guided biopsy system to integrate with SM. The dual modality breast biopsy system combines the advantages of both approaches with 3D US and SM targeting, near real-time 3D and real-time 2D US guidance, breast stabilisation and a confined needle trajectory. Our goal is to be able to biopsy a larger percentage of suspicious masses using ultrasound, by clarifying ambiguous structures with mammographic imaging. Using breast phantoms, we have shown that our ultrasound guided biopsy system was capable of targeting artificial lesions that were 3.2 mm in diameter, with a 96% success rate. Through this study, we also demonstrated that our system was equivalent to current clinical practice, for an in vitro biopsy task. Metal beads in known relative positions allowed us to determine the geometry of the SM system, so that stereotactic mammography could be registered to 3D US images. The target registration error was found to be 1.6 mm. This error was dominated by positioning error in the vertical direction (perpendicular to the film surface). As an adjunct to SM, we propose that 3D US could provide more complete imaging information for target identification and real-time monitoring of needle insertion, as well as providing a means for rapid confirmation of biopsy success.     

A definitive synthesis of D-myo-inositol 1,4,5,6-tetrakisphosphate and its enantiomer D-myo-inositol 3,4,5,6-tetrakisphosphate from a novel butane-2,3-diacetal-protected inositol

New and rapid syntheses of the enantiomeric intracellular signalling molecules d-myo-inositol 1,4,5,6-tetrakisphosphate (1 a) and D-myo-inositol 3,4,5,6-tetrakisphosphate (1 b) are described. The synthetic strategy employs the novel butane-2,3-diacetal-protected (BDA-protected) myo-inositol (+/-)-3 ab, directly accessible from myo-inositol on a large scale, and an optical resolution with diastereoisomeric (R)-(-)-acetylmandelate esters. The X-ray crystal structure of (+/-)-4, an unusual side product of acid-catalysed reaction of myo-inositol with butanedione is also presented, and the absolute configurations of 1 a and 1 b are definitively assigned by conversion of key precursors into (+)-bornesitol and L-iditol hexaacetate, respectively. Biological activity of synthetic 1 b was confirmed in comparison with the natural polyphosphate.     

Regioselective synthesis of 3,3‐diethyl‐4‐(methylene)‐1‐quinol‐2‐ones by an intramolecular microwave assisted heck reaction

A protocol for the intramolecular Heck cyclization to afford 3,3‐diethyl‐4‐(methylene)‐1‐quinol‐2‐ones is described. We observed that the use of microwave irradiation increased the efficiency of the reaction. Several examples are presented which show the versatility of the reaction.     

Three-dimensional hydrogen-bond geometry and probability information from a crystal survey

Summary An extensive crystal survey of the Cambridge Structural Database has been carried out to provide hydrogen-bond data for use in drug-design strategies. Previous crystal surveys have generated 1D frequency distributions of hydrogen-bond distances and angles, which are not sufficient to model the hydrogen bond as a ligand-receptor interaction. For each hydrogen-bonding group of interest to the drug designer, geometric hydrogen-bond criteria have been derived. The 3D distribution of complementary atoms about each hydrogen-bonding group has been ascertained by dividing the space about each group into bins of equal volume and counting the number of observed hydrogen-bonding contacts in each bin. Finally, the propensity of each group to form a hydrogen bond has been calculated. Together, these data can be used to predict the potential site points with which a ligand could interact and there-fore could be used in molecular-similarity studies, pharmacophore query searching of databases, or de novo design algorithms.     

Characterisation of the photocatalyst Pilkington Activ™: a reference film photocatalyst?

Pilkington Glass Activ™ represents a possible suitable successor to P25 TiO₂, especially as a benchmark photocatalyst film for comparing other photocatalyst or PSH self-cleaning films. Activ™ is a glass product with a clear, colourless, effectively invisible, photocatalytic coating of titania that also exhibits PSH. Although not as active as a film of P25 TiO₂, Activ™ vastly superior mechanical stability, very reproducible activity and widespread commercial availability makes it highly attractive as a reference photocatalytic film. The photocatalytic and photo-induced superhydrophilitic (PSH) properties of Activ™ are studied in some detail and the results reported. Thus, the kinetics of stearic acid destruction (a 10⁴ electron process) are zero order over the stearic acid range 4–129 monolayers and exhibit formal quantum efficiencies (FQE) of 0.7×10⁻⁵ and 10.2×10⁻⁵ molecules per photon when irradiated with light of 365±20 and 254 nm, respectively; the latter appears also to be the quantum yield for Activ™ at 254 nm. The kinetics of stearic acid destruction exhibit Langmuir–Hinshelwood-like saturation type kinetics as a function of oxygen partial pressure, with no destruction occurring in the absence of oxygen and the rate of destruction appearing the same in air and oxygen atmospheres. Further kinetic work revealed a Langmuir adsorption type constant for oxygen of 0.45±0.16 kPa⁻¹ and an activation energy of 19±1 kJ mol⁻¹. A study of the PSH properties of Activ™ reveals a high water contact angle (67°) before ultra-bandgap irradiation reduced to 0° after prolonged irradiation. The kinetics of PSH are similar to those reported by others for sol–gel films using a low level of UV light. The kinetics of contact angle recovery in the dark appear monophasic and different to the biphasic kinetics reported recently by others for sol–gel films [J. Phys. Chem. B 107 (2003) 1028]. Overall, Activ™ appears a very suitable reference material for semiconductor film photocatalysis.     

Photogeneration of Silver Particles in PVA Fibers and Films

Fibers and films prepared from blends of poly(vinyl alcohol) and poly(acrylic acid) were found to be suitable matrices for the solid-state photoreduction of silver ions in the presence of air. Fast generation of nanometer-sized silver crystallites was observed when fibers of polymer blends crosslinked with dimethyl sulfoxide were irradiated with 350nm light. Optical determinations of the formation kinetics were carried out using thin films of noncrosslinked as well as lightly and heavily crosslinked polymer blends. Small Ag clusters were detected initially, which were stable in the dark but transformed into larger metal particles upon further illumination. Both formation processes occurred only under high light intensity illumination and the kinetic data were inconsistent with monophotonic mechanisms.     

Preparation of Enantiomerically Pure β-Silylcarboxyl Derivatives by Asymmetric 1,4-Addition to N-Enoyl-sultams. Preliminary Communication

EtAlCl₂-promoted additions of organocopper reagents to camphor-derived, conjugated N-enoyl-sultams gave saturated and olefinic β-silylcarboxyl derivatives with high diastereodifferentiation. Nondestructive removal of the chiral auxiliary followed by oxidative Si-C bond cleavage furnished enantiomerically pure acetate-derived aldols and propionate-derived ‘anti’ -aldols (via silyl-directed α-methylation).