Comparison of two models for managing reliability growth during product design

Relying on reliability growth testing to improve system designis neither usually effective nor efficient. Instead it is importantto design in reliability. This requires models to estimate reliabilitygrowth in the design that can be used to assess whether goalreliability will be achieved within the target timescale forthe design process. Many models have been developed for analysisof reliability growth on test, but there has been much lessattention given to reliability growth in design. This paperdescribes and compares two models: one motivated by the practicalengineering process; the other by extending the reasoning ofstatistical reliability growth modelling. Both models are referencedin the recently revised edition of international standard IEC61164. However, there has been no reported evaluation of theirproperties. Therefore, this paper explores the commonalitiesand differences between these models through an assessment oftheir logic and their application to an industrial example.Recommendations are given for the use of reliability growthmodels to aid management of the design process and to informproduct development.     

Synthesis of oxazolidinedione derived bicalutamide analogs

The synthesis of chiral oxazolidinedione derived bicalutamide analogs has been discussed.     

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.     

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.     

SN2 reactions in the gas phase. Structure of the transition state

The alkylhalide-halide association ions, [RX₂]^? that are observed in the negative chemical ionization mass spectra of alkyl halides appear to be directly related to the corresponding S_N2 transition states in solution. ‘Frontside’ association of halide ions with bridgehead alkyl halides does not occur in our system. The Change in heats and entropies of association for the chloromethane series is consistent with delocalization in the [RX]₂^? ions.     

Stereoselective reductase-catalysed deoxygenation of sulfoxides in aerobic and anaerobic bacteria

Direct and indirect evidence, of unexpected stereoselective reductase-catalysed deoxygenations of sulfoxides, was found. The deoxygenations proceeded simultaneously, with the expected dioxygenase-catalysed asymmetric sulfoxidation of sulfides, during some biotransformations with the aerobic bacterium Pseudomonas putida UV4. Stereoselective reductase-catalysed asymmetric deoxygenation of racemic alkylaryl, dialkyl and phenolic sulfoxides was observed, without evidence of the reverse sulfoxidation reaction, using anaerobic bacterial strains. A purified dimethyl sulfoxide reductase, obtained from the intact cells of the anaerobic bacterium Citrobacter braakii DMSO 11, yielded, from the corresponding racemates, enantiopure alkylaryl sulfoxide and thiosulfinate samples.     

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.     

Long-range fluorine-proton coupling in 1,2,4-triazole derivatives

Several 1,2,4-triazole derivatives containing a 2-fluorophenyl substituent at either the 3- or 5-position and a methyl group at the 4-position were synthesized. These derivatives exhibit long-range ¹⁹F-¹H and ¹⁹F-¹³C through-space coupling in their ¹H and ¹³C nmr spectra between the fluorine and the 4-methyl group. The close spatial proximity of these nuclei was confirmed by X-ray analysis and by fluorine irradiated proton observe ({¹⁹F}-¹H) NOE difference spectroscopy.     

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.