Chemical autocatalysis in the NO + CO reaction on Pt(100)

It is shown that the reaction between NO and CO on Pt(100) is autocatalytic and probably involves a surface species which accelerates the reaction. Temperature-programmed desorption (TPD) of co-adsorbed NO and CO yields complete reaction, with N₂ and CO₂ desorbing simultaneously in sharp peaks at ≈410 K. Isothermal desorption also yields rates characteristic of chemical autocatalysis.     

Cost–benefit modelling for reliability growth

Decisions during the reliability growth development process of engineering equipment involve trade-offs between cost and risk. However slight, there exists a chance an item of equipment will not function as planned during its specified life. Consequently the producer can incur a financial penalty. To date, reliability growth research has focussed on the development of models to estimate the rate of failure from test data. Such models are used to support decisions about the effectiveness of options to improve reliability. The extension of reliability growth models to incorporate financial costs associated with ‘unreliability’ is much neglected. In this paper, we extend a Bayesian reliability growth model to include cost analysis. The rationale of the stochastic process underpinning the growth model and the cost structures are described. The ways in which this model can be used to support cost–benefit analysis during product development are discussed and illustrated through a simple case.     

BMO from dyadic BMO via expectations on product spaces of homogeneous type

Using the random dyadic lattices developed by Hytönen and Kairema, we build up a bridge between BMO and dyadic BMO, and hence one between VMO and dyadic VMO, via expectations over dyadic lattices on spaces of homogeneous type, including both the one-parameter and product cases. We also obtain a similar relationship between _Ap$A_p$ and dyadic _Ap$A_p$, as well as one between the reverse Hölder class _RHp${\mathit{RH}}_p$ and dyadic _RHp${\mathit{RH}}_p$, via geometric–arithmetic expectations. These results extend the earlier theory along this line, developed by Garnett, Jones, Pipher, Ward, Xiao and Treil, to the more general setting of spaces of homogeneous type in the sense of Coifman and Weiss.     

Analysis of the hydrogen and oxygen stable isotope ratios of beverage waters without prior water extraction using isotope ratio infrared spectroscopy

Hydrogen (δ²H) and oxygen (δ¹⁸O) stable isotope analysis is useful when tracing the origin of water in beverages, but traditional analytical techniques are limited to pure or extracted waters. We measured the isotopic composition of extracted beverage water using both isotope ratio infrared spectroscopy (IRIS; specifically, wavelength‐scanned cavity ring‐down spectroscopy) and isotope ratio mass spectrometry (IRMS). We also analyzed beer, sodas, juices, and milk ‘as is’ using IRIS. For IRIS analysis, four sequential injections of each sample were measured and data were corrected for sample‐to‐sample memory using injections (a) 1‐4, (b) 2‐4, and (c) 3‐4. The variation between δ²H and δ¹⁸O values calculated using the three correction methods was larger for unextracted (i.e., complex) beverages than for waters. The memory correction was smallest when using injections 3‐4. Beverage water δ²H and δ¹⁸O values generally fit the Global Meteoric Water Line, with the exception of water from fruit juices. The beverage water stable isotope ratios measured using IRIS agreed well with the IRMS data and fit 1:1 lines, with the exception of sodas and juices (δ²H values) and beers (δ¹⁸O values). The δ²H and δ¹⁸O values of waters extracted from beer, soda, juice, and milk were correlated with complex beverage δ²H and δ¹⁸O values (r = 0.998 and 0.997, respectively) and generally fit 1:1 lines. We conclude that it is possible to analyze complex beverages, without water extraction, using IRIS although caution is needed when analyzing beverages containing sugars, which can clog the syringe and increase memory, or alcohol, a known spectral interference. Copyright © 2010 John Wiley & Sons, Ltd.     

Vitamin B12 as an allosteric cofactor; dual fluorescence, hysteresis, oscillations and the selection of corrin over porphyrin

Studies of the emission spectra of four Co(III) cobinamides (diaquo-, aquohydroxo-, dihydroxo- and dicyano-) show (1) that the excited states corresponding to the alphabeta and epsilon absorption bands behave like the S(1) and S(2) levels in the non-alternant hydrocarbon azulene (with emission from S(2)> S(1) in violation of Kasha's rule) and (2) that the excited states include a TICT (twisted intramolecular charge transfer) mechanism, as in the simpler cyanines, but where the TICT state gives rise to dual fluorescence instead of cis-trans isomerisation. Combined with the previously reported dual fluorescence from the S(1) level in synthetic metal corrinoids and in the naturally-occurring metal-free corrin, this provides evidence that the existence of an additional (metastable) ground state with a significantly different vibronic splitting and nuclear configuration is an intrinsic property of the basic corrin ligand (irrespective of the nature of the side-chains and the metal ion or even the absence of a metal) which distinguishes it from porphyrin. The occurrence of hysteresis (and its associated oscillations) in redox reactions of the cobinamides involving both the Co(III/II) and Co(II/I) couples indicates that the corrin ligand also has an intrinsic ability to exist in different conformations or "allosteric" forms with differing redox potential, which further distinguishes it from the porphyrin ligand. Possible links between the existence of an additional metastable ground state and of allosteric changes and the likely reasons for the selection of corrin over a porphyrin for the vitamin B(12)-dependent enzymes are discussed.     

Ruthenium bipyridyl compounds with two terminal alkynyl ligands

Compounds of the form Ru(X2bipy)(PPh3)2(-C triple bond CC6H4NO2-p)2(X2bipy = 4,4'-X(2)-2,2'-bipyridine, X = Me 3a, Br 3b, I 3c) have been synthesised from the mono-alkynyl precursors Ru(X2bipy)(PPh3)2(-C triple bond CC6H4NO2-p)Cl (X = Me 2a, Br 2b, I 2c); the former are the first ruthenium bis-alkynyl compounds that also contain a bipyridyl ligand. Spectroelectrochemical investigation of 3a shows that the metal is readily oxidised to form the ruthenium(III) compound 3a+, and will also undergo a single-electron reduction at each nitro group to form 3a2-. ESR and UV/visible spectra of these redox congeners are presented. We also report the synthesis of [Ru(Me2bipy)(PPh3)2(-C triple bond CBut)(N triple bond N)][PF6] during the attempted synthesis of Ru(Me2bipy)(PPh3)2(-C triple bond CBut)2, and report its X-ray crystal structure and IR spectrum. X-Ray crystal structures of 3b and 3c(as two different solvates) are presented, and the nature of the intermolecular interactions seen therein is discussed. Z-Scan measurements on Ru(Me2bipy)(PPh3)2(-C triple bond CR)Cl (R = C6H4NO2-p2a, But, Ph, C6H4Me) are also reported, and show that Ru(Me2bipy)(PPh3)2(-C triple bond CR)Cl (R = C6H4NO2-p2a, Ph) exhibit moderate third-order non-linearities.     

Evaluation of C4 diphosphine ligands in rhodium catalysed methanol carbonylation under a syngas atmosphere: synthesis, structure, stability and reactivity of rhodium(I) carbonyl and rhodium(III) acetyl intermediates

The carbonylation of methanol to acetic acid is a hugely important catalytic process, and there are considerable cost and environmental advantages if a process could be designed that was tolerant of hydrogen impurities in the CO feed gas, while eliminating by-products such as propionic acid and acetaldehyde altogether. This paper reports on an investigation into the application of rhodium complexes of several C(4) bridged diphosphines, namely BINAP, 1,4-bis(diphenylphosphino)butane (dppb), bis(diphenylphosphino)xylene (dppx) and 1,4-bis(dicyclohexylphosphino)butane (dcpb) as catalysts for hydrogen tolerant methanol carbonylation. An investigation into the structure, reactivity and stability of pre-catalysts and catalyst resting states of these complexes has also been carried out in order to understand the observations in catalysis. Rh(I) carbonyl halide complexes of each of the ligands have been prepared from both [Rh(2)(CO)(4)Cl(2)] and dimeric mu-Cl-[Rh(L)Cl](2) complexes. These Rh(I) carbonyl complexes are either dimeric with bridging phosphine ligands (dppb, dcpb, dppx) or monomeric chelate complexes. The reaction of the complexes with methyl iodide at 140 degrees C has been studied, which has revealed clear differences in the stability of the corresponding Rh(III) complexes. Surprisingly, the dimeric Rh(I) carbonyls react cleanly with MeI with rearrangement of the diphosphine to a chelate co-ordination mode to give stable Rh(III) acetyl complexes. The Rh acetyls for L=dppb and dppx have been fully characterised by X-ray crystallography. During the catalytic studies, the more rigid dppx and BINAP ligands were found to be nearly 5 times more hydrogen tolerant than [Rh(CO)(2)I(2)](-), as revealed by by-product analysis. The origin of this hydrogen tolerance is explained based on the differing reactivities of the Rh acetyls with hydrogen gas, and by considering the structure of the complexes.     

Acrylamide analysis: assessment of results from six rounds of Food Analysis Performance Assessment Scheme (FAPAS) proficiency testing

Six proficiency tests have now been completed in an ongoing program of the UK Food Analysis Performance Assessment Scheme (FAPAS) for the analysis of acrylamide in a range of food matrixes. Homogeneous test material samples were requested by laboratories throughout the world, with 29 to 45 submitting results for each test. Results were analyzed by appropriate statistical procedures, and z-scores were awarded for reported values. In the absence of both legislation and collaborative trial data, the target standard deviation was derived from the Horwitz equation, although it is acknowledged that there is a need to establish a "fit for purpose" target standard deviation specifically for acrylamide analysis. Participants were encouraged to use the analytical method routinely used in their own laboratory and to provide details of their procedure. Close examination of the data submitted indicates that performance is generally acceptable in terms of accuracy. There is no significant difference between results submitted by gas chromatography and liquid chromatography (GC and LC) methods, and no method dependency on the use of internal standards or sample size. However, choice of extraction solvent may be important, with indications that plain water is an acceptable extraction method. There is evidence from the most recent test that direct (underivatized) GC methodology may present problems, but more data are required and this aspect will be monitored in the continuing proficiency testing program.     

CGC using a programmable electronic pressure controller

Capillary gas chromatographic separations were performed with an electronic pressure control system developed to provide precise closed-loop control of inlet pressure through the use of a solid state micro-machined pressure sensor and electronically controlled proportional valve. The closed-loop control of the electronic system provided better precision than the open-loop control achieved by manual pressure regulation. Closed-loop control can perform pressure programming, which can be combined with temperature programming to optimize separations. The pressure sensor monitors the integrity of the flow system and singals the controller to reduce flow in the presence of a sudden loss of system pressure.