Ion chromatographic precision measurement procedure for electrolytes in human serum: validation with the aid of primary measurement procedures

In order to make analytical measurement results traceable to the SI units in the field of clinical chemistry, an ion chromatographic (IC) measurement procedure has been developed which allows the amount of substance of the four so-called electrolytes Na, K, Mg and Ca as well as that of Li to be determined efficiently in human serum and with high accuracy. The IC measurement procedure was validated using primary measurement procedures confirmed by international comparison measurements and is proposed for use as a transfer standard when comparing measurements with clinical reference laboratories. The solutions used for calibration were gravimetrically prepared from pure substances (salts). Their chemical compositions had been iteratively fitted to those of the samples. The serum samples were mineralized by microwave-assisted digestion. The following relative expanded uncertainties for the average elemental contents were obtained: Li 0.4%, Na 0.14%, K 0.6%, Mg 0.8% and Ca 0.4%.     

Car-Parrinello molecular dynamics study of the rearrangement of the valeramide radical cation

Car-Parrinello molecular dynamics (CPMD) studies of neutral (1) and ionized (1 (+.)) valeramide are performed with the aim of providing a rationalization for the unusual temperature effect on the dissociation pattern of 1(+.) observed in mass spectrometric experiments. According to CPMD simulations of neutral valeramide 1 performed at approximately 500 K, the conformation with the fully relaxed carbon backbone predominates (96 %). Conformational changes involving folding of the carbon backbone into conformers that would allow intramolecular H transfers are predicted not to take place spontaneously at this temperature because of the barrier heights associated with these transitions (3.5 and 6.9 kcal mol(-1)), which cannot be overcome by thermal motion alone. For 1(+.), CPMD simulations performed at approximately 300 K reveal a substantial stability of a conformation in which the carbon backbone is fully relaxed; no reaction is observed even after 7 ps. However, when conformers with already folded carbon-backbones are used as initial geometries in the CPMD simulations, the gamma-hydrogen migration (McLafferty rearrangement resulting in C(3)H(6)) is already completed within 2 ps. For this important process, the free activation energy associated with both a required conformational change and the subsequent H transfer equals 4.5 kcal mol(-1), while for the formally related delta-H shift (which eventually gives rise to the elimination of C(2)H(4)/C(2)H(5.)) it amounts to 7.0 kcal mol(-1). Since the barriers associated with conformational changes are energetically more demanding than those of the corresponding hydrogen transfers, 1(+.) is essentially trapped by conformational barriers and long-lived at approximately 300 K. At elevated temperatures (500 K), the preferred reaction (within 7.3 ps) in the CPMD simulation corresponds to the McLafferty rearrangement. The estimated free activation energy associated with this process amounts to 2.5 kcal mol(-1), while the free activation energy for the delta-H transfer equals 4.4 kcal mol(-1). This relatively small free activation energy for the McLafferty rearrangement might cause dissociation of a substantial fraction of 1(+.) prior to the time-delayed mass selection, which would reduce the C3/C2 ratio in the experiments conducted with metastable ions that have a lifetime in the order of some micros at a source temperature of 500 K.     

The Major/Minor Concept: Dependence of the Selectivity of Homogeneously Catalyzed Reactions on Reactivity Ratio and Concentration Ratio of the Intermediates

The homogeneously catalyzed asymmetric hydrogenation of prochiral olefins with cationic Rh^I complexes is one of the best‐understood selection processes. For some of the catalyst/substrate complexes, experimental proof points out the validation of the major/minor principle; the concentration‐deficient minor substrate complex, which has very high reactivity, yields the excess enantiomer. As exemplified by the reaction system of [Rh(dipamp)(MeOH)₂]⁺/methyl (Z)‐α‐acetamidocinnamate (dipamp=1,2‐bis((o‐methoxyphenyl)phenylphosphino)ethane), all six of the characteristic reaction rate constants have been previously identified. Recently, it was found that the major substrate complex can also yield the major enantiomer (lock‐and‐key principle). The differential equation system that results from the reaction sequence can be solved numerically for different hydrogen partial pressures by including the known equilibrium constants. The result displays the concentration–time dependence of all species that exist in the catalytic cycle. On the basis of the known constants as well as further experimental evidence, this work focuses on the examination of all principal possibilities resulting from the reaction sequence and leading to different results for the stereochemical outcome. From the simulation, the following conclusions can be drawn: 1) When an intermediate has extreme reactivity, its stationary concentration can become so small that it can no longer be the source of product selectivity; 2) in principle, the major/minor and lock‐and‐key principles can coexist depending on the applied pressure; 3) thermodynamically determined intermediate ratios can be completely converted under reaction conditions for a selection process; and 4) the increase in enantioselectivity with increasing hydrogen partial pressure, a phenomenon that is experimentally proven but theoretically far from being well‐understood, can be explained by applying both the lock‐and‐key as well as the major/minor principle.     

Genetic algorithm-based subproblem solution procedures for a modified shifting bottleneck heuristic for complex job shops

In this paper, we consider a modified shifting bottleneck heuristic for complex job shops. The considered job shop environment contains parallel batching machines, machines with sequence-dependent setup times and reentrant process flows. Semiconductor wafer fabrication facilities (Wafer Fabs) are typical examples for manufacturing systems with these characteristics. Our primary performance measure is total weighted tardiness (TWT). The shifting bottleneck heuristic uses a disjunctive graph to decompose the overall scheduling into scheduling problems for single tool groups. The scheduling algorithms for these scheduling problems are called subproblem solution procedures (SSPs). In previous research, only subproblem solution procedures based on dispatching rules have been considered. In this paper, we are interested in how much we can gain in terms of TWT if we apply more sophisticated subproblem solution procedures like genetic algorithms for parallel machine scheduling. We conduct simulation experiments in a dynamic job shop environment in order to assess the performance of the suggested subproblem solution procedures. It turns out that using near to optimal subproblem solution procedures leads in many situations to improved results compared to dispatching-based subproblem solution procedures.     

On the Weak Measurement of Velocity in Bohmian Mechanics

In a recent article (Wiseman in New J. Phys. 9:165, 2007), Wiseman has proposed the use of so-called weak measurements for the determination of the velocity of a quantum particle at a given position, and has shown that according to quantum mechanics the result of such a procedure is the Bohmian velocity of the particle. Although Bohmian mechanics is empirically equivalent to variants based on velocity formulas different from the Bohmian one, and although it has been proven that the velocity in Bohmian mechanics is not measurable, we argue here for the somewhat paradoxical conclusion that Wiseman’s weak measurement procedure indeed constitutes a genuine measurement of velocity in Bohmian mechanics. We reconcile the apparent contradictions and elaborate on some of the different senses of measurement at play here.