ConFlo III - an interface for high precision delta(13)C and delta(15)N analysis with an extended dynamic range

A newly developed interface coupling a CHN combustion device (elemental analyser 'EA') to an isotope ratio mass spectrometer is described and evaluated. The purpose of the device is to extend the dynamic range of delta(13)C and delta(15)N analysis from less than 2 orders of magnitude to more than 3 orders of magnitude. Carbon isotope ratio measurements of atropine as a model compound have been performed analysing between 1 μg to 5 mg C with acceptable to excellent precision (0.6 to 0.06 per thousand, delta-notation). The correction due to the blank signal is critical for sample amounts smaller than 4 μg C. The maximum sample weight is determined by the combustion capacity of the EA. Larger sample amounts are measured using dilution of a small part of the EA effluent with helium. The dilution mechanism works virtually free of isotope fractionation. Copyright 1999 John Wiley & Sons, Ltd.     

Coinage metal aluminyl complexes: probing regiochemistry and mechanism in the insertion and reduction of carbon dioxide

The synthesis of coinage metal aluminyl complexes, featuring M–Al covalent bonds, is reported via a salt metathesis approach employing an anionic Al(i) (‘aluminyl’) nucleophile and group 11 electrophiles. This approach allows access to both bimetallic (1 : 1) systems of the type (^tBu₃P)MAl(NON) (M = Cu, Ag, Au; NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene) and a 2 : 1 di(aluminyl)cuprate system, K[Cu{Al(NON)}₂]. The bimetallic complexes readily insert heteroallenes (CO₂, carbodiimides) into the unsupported M–Al bonds to give systems containing a M(CE₂)Al bridging unit (E = O, NR), with the μ-κ¹(C):κ²(E,E′) mode of heteroallene binding being demonstrated crystallographically for carbodiimide insertion in the cases of all three metals, Cu, Ag and Au. The regiochemistry of these processes, leading to the formation of M–C bonds, is rationalized computationally, and is consistent with addition of CO₂ across the M–Al covalent bond with the group 11 metal acting as the nucleophilic partner and Al as the electrophile. While the products of carbodiimide insertion are stable to further reaction, their CO₂ analogues have the potential to react further, depending on the identity of the group 11 metal. (^tBu₃P)Au(CO)₂Al(NON) is inert to further reaction, but its silver counterpart reacts slowly with CO₂ to give the corresponding carbonate complex (and CO), and the copper system proceeds rapidly to the carbonate even at low temperatures. Experimental and quantum chemical investigations of the mechanism of the CO₂ to CO/carbonate transformation are consistent with rate-determining extrusion of CO from the initially-formed M(CO)₂Al fragment to give a bimetallic oxide that rapidly assimilates a second molecule of CO₂. The calculated energetic barriers for the most feasible CO extrusion step (ΔG^‡ = 26.6, 33.1, 44.5 kcal mol⁻¹ for M = Cu, Ag and Au, respectively) are consistent not only with the observed experimental labilities of the respective M(CO)₂Al motifs, but also with the opposing trends in M–C (increasing) and M–O bond strengths (decreasing) on transitioning from Cu to Au.

The differential reactivity of copper, silver and gold aluminyl compounds towards CO₂ and other heteroallenes are probed by experimental and quantum chemical methods.     

Intramolecular pi-dimerization in a 1,1'-bis(verdazyl)ferrocene diradical

The solid state structure of 1,1'-bis(verdazyl)ferrocene reveals the two radical moieties associated intramolecularly to give the first example of a pi-dimer of a stable verdazyl radical. The pi-dimer structure is not maintained in solution. Magnetic characterization indicates that the radicals are sufficiently strongly antiferromagnetically coupled so as to render the molecule diamagnetic at room temperature.     

Laser-driven shock experiments on precompressed water: Implications for "icy" giant planets

Laser-driven shock compression of samples precompressed to 1 GPa produces high-pressure-temperature conditions inducing two significant changes in the optical properties of water: the onset of opacity followed by enhanced reflectivity in the initially transparent water. The onset of reflectivity at infrared wavelengths can be interpreted as a semiconductor<-->electronic conductor transition in water, and is found at pressures above approximately 130 GPa for single-shocked samples precompressed to 1 GPa. Our results indicate that conductivity in the deep interior of "icy" giant planets is greater than realized previously because of an additional contribution from electrons.     

Near-thermal reactions of Au(+)(1S,3D) with CH3X (X = F,Cl)

Reactions of Au(+)((1)S) and Au(+)((3)D) with CH(3)F and CH(3)Cl have been carried out in a drift cell in He at a pressure of 3.5 Torr at both room temperature and reduced temperatures in order to explore the influence of the electronic state of the metal on reaction outcomes. State-specific product channels and overall two-body rate constants were identified using electronic state chromatography. These results indicate that Au(+)((1)S) reacts to yield an association product in addition to AuCH(2)(+) in parallel steps with both neutrals. Product distributions for association vs HX elimination were determined to be 79% association/21% HX elimination for X = F and 50% association/50% HX elimination when X = Cl. Reaction of Au(+)((3)D) with CH(3)F also results in HF elimination, which in this case is thought to produce (3)AuCH(2)(+). With CH(3)Cl, Au(+)((3)D) reacts to form AuCH(3)(+) and CH(3)Cl(+) in parallel steps. An additional product channel initiated by Au(+)((3)D) is also observed with both methyl halides, which yields CH(2)X(+) as a higher-order product. Kinetic measurements indicate that the reaction efficiency for both Au(+) states is significantly greater with CH(3)Cl than with CH(3)F. The observed two-body rate constant for depletion of Au(+)((1)S) by CH(3)F represents less than 5% of the limiting rate constant predicted by the average dipole orientation model (ADO) at room temperature and 226 K, whereas CH(3)Cl reacts with Au(+)((1)S) at the ADO limit at both room temperature and 218 K. Rate constants for depletion of Au(+)((3)D) by CH(3)F and CH(3)Cl were measured at 226 and 218 K respectively, and indicate that Au(+)((3)D) is consumed at approximately 2% of the ADO limit by CH(3)F and 69% of the ADO limit by CH(3)Cl. Product formation and overall efficiency for all four reactions are consistent with previous experimental results and available theoretical models.     

A collaboration into research on nanoparticles (ACORN)

This paper describes the operation and outcome of one of the United Kingdom's largest multi-partner research activities in nanoparticles.The research covers the discovery and development of organic and inorganic crystals/nanoparticles,nanoparticle properties towards specific product applications,The research also encompassed bespoke measurement technology for nanoparticles and structure interactions.Significant research outcomes are summarised.The paper illustrates the advantages from industrially motivated research and value of collective action between a broad group of researchers in a nation.     

Bose-Einstein correlations in neutrino and antineutrino interactions in deuterium

Bose-Einstein correlations between pions of equal charge have been observed in Charged Current and Neutral Current (anti)neutrino-deuterium interactions in the BEBC bubble chamber exposed to the SPS wide band beam. The pion emission region is found to be essentially spherical with a mean radius of (0.48±0.07) fm; the chaoticity parameter is 0.36±0.04.     

Bias-dependent spin relaxation in a -InAs/AlSb 2DES

Manipulation of electron spin is a critical component of many proposed semiconductor spintronic devices. One promising approach utilizes the Rashba effect by which an applied electric field can be used to reduce the spin lifetime or rotate spin orientation through spin–orbit interaction. The large spin–orbit interaction needed for this technique to be effective typically leads to fast spin relaxation through precessional decay, which may severely limit device architectures and functionalities. An exception arises in [1 1 0]-oriented heterostructures where the crystal magnetic field associated with bulk inversion asymmetry lies along the growth direction and in which case spins oriented along the growth direction do not precess. These considerations have led to a recent proposal of a spin-FET that incorporates a [1 1 0]-oriented, gate-controlled InAs quantum well channel. We report measurements of the electron spin lifetime as a function of applied electric field in a [1 1 0]-InAs 2DES. Measurements made using an ultrafast, mid-IR pump-probe technique indicate that the spin lifetime can be reduced from its maximum to minimum value over a range of less than 0.2 V per quantum well at room temperature.