A simple and universal method for the separation and identification of phospholipid molecular species

One of the major challenges in lipidomics is to obtain as much information about the lipidome as possible. Here, we present a simple yet universal high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) method to separate molecular species of all phospholipid classes in one single run. The method is sensitive, robust and allows lipid profiling using full scan mass spectrometry, as well as lipid class specific scanning in positive and negative ionisation mode. This allows high-throughput processing of samples for lipidomics, even if different types of MS analysis are required. Excellent separation of isobaric and even isomeric species is achieved, and original levels of lyso-lipids can be determined without interference from lyso-lipids formed from diacyl species by source fragmentation. As examples of application of this method, more than 400 phospholipid species were identified and quantified in crude phospholipid extracts from rat liver and the parasitic helminth Schistosoma mansoni.     

On queues with service and interarrival times depending on waiting times

We consider an extension of the standard G/G/1 queue, described by the equation $W\stackrel{ \mathcal {D}}{=}\max\mathrm{max}\,\{0,B-A+YW\}$ , where ?[Y=1]=p and ?[Y=?1]=1?p. For p=1 this model reduces to the classical Lindley equation for the waiting time in the G/G/1 queue, whereas for p=0 it describes the waiting time of the server in an alternating service model. For all other values of p, this model describes a FCFS queue in which the service times and interarrival times depend linearly and randomly on the waiting times. We derive the distribution of W when A is generally distributed and B follows a phase-type distribution, and when A is exponentially distributed and B deterministic.     

Advanced data analysis and process monitoring across manufacturing plants using multilevel methods

Three‐level versions of Multilevel Simultaneous Component Analysis (MLSCA) and Multilevel Partial Least Squares (MLPLS) were developed, which are capable of separating between‐plant, between‐run and within‐run process variation, and modeling these three levels in a multivariate way. In comparison to the two‐level versions they allow to discriminate between overall differences between plants and the variation between runs within a plant. It was shown that the three‐level version of MLSCA has clear added value for the analysis of process runs from different plants. In MLPLS other projections of the multivariate data onto latent variables and different views of the data are obtained when relevant Y information is available. This has clear added value for obtaining insight into the relation between process data and Y. A special use of MLPLS is to diagnose aberrations in first principles models. In batch process monitoring MLSCA at three levels allows simultaneous multivariate modelling of batch data from different manufacturing plants. By filtering out the between‐plant and between‐run sources of variation, and using only within‐run variation, monitoring models can be improved. Using within‐run data, it is possible to build monitoring models across manufacturing units and reduce the number of nuisance alarms, while improving abnormal situation detection and diagnosis. Model transfer is only possible if static between‐plant differences exist, but not if there are dynamic differences.     

Elucidating Zeolite Channel Geometry–Reaction Intermediate Relationships for the Methanol-to-Hydrocarbon Process

The chemical industry has exploited zeolite shape selectivity for more than 50 years, yet our fundamental understanding remains incomplete. Herein, the zeolite channel geometry–reactive intermediate relationships are studied in detail using anisotropic zeolite ZSM-5 crystals for the methanol-to-hydrocarbon (MTH) process, and advanced magic-angle spinning solid-state NMR (ssNMR) spectroscopy. The utilization of anisotropic ZSM-5 crystals enabled the preferential formation of reaction intermediates in single-orientation zeolite channels, as revealed by molecular dynamics simulations and in situ UV/Vis diffuse-reflectance spectroscopy. The ssNMR results show that the slightly more constrained sinusoidal zeolite channels favor the olefin cycle by promoting the homologation of alkanes, whereas the more extended straight zeolite channels facilitate the aromatic cycle with a higher degree of alkylation of aromatics. Dynamic nuclear polarization experiments further indicate the preferential formation of heavy aromatics at the zeolite surface dominated by the sinusoidal channels, providing further insight into catalyst deactivation.     

Queue lengths and workloads in polling systems

For a single-server multi-station polling system, we focus on the generating function and Laplace–Stieltjes transform of the time-stationary joint queue length and workload distributions, respectively, under no further assumptions on the service discipline. We express these quantities as expressions involving the generating functions of the joint queue length distribution at visit beginnings and visit completions at the various stations. The latter is known for a broad variety of cases. Finally, we identify a workload decomposition result.     

Estimate on the Pathwise Lyapunov Exponent of Linear Stochastic Differential Equations with Constant Coefficients

In this article, we study the problem of estimating the pathwise Lyapunov exponent for linear stochastic systems with multiplicative noise and constant coefficients. We present a Lyapunov type matrix inequality that is closely related to this problem, and show under what conditions we can solve the matrix inequality. From this we can deduce an upper bound for the Lyapunov exponent. In the converse direction, it is shown that a necessary condition for the stochastic system to be pathwise asymptotically stable can be formulated in terms of controllability properties of the matrices involved.     

Tandem Queues with Impatient Customers for Blood Screening Procedures

We study a blood testing procedure for detecting viruses like HIV, HBV and HCV. In this procedure, blood samples go through two screening steps. The first test is ELISA (antibody Enzyme Linked Immuno-Sorbent Assay). The portions of blood which are found not contaminated in this first phase are tested in groups through PCR (Polymerase Chain Reaction). The ELISA test is less sensitive than the PCR test and the PCR tests are considerably more expensive. We model the two test phases of blood samples as services in two queues in series; service in the second queue is in batches, as PCR tests are done in groups. The fact that blood can only be used for transfusions until a certain expiration date leads, in the tandem queue, to the feature of customer impatience. Since the first queue basically is an infinite server queue, we mainly focus on the second queue, which in its most general form is an S-server M/G ^[k,?K]/S?+?G queue, with batches of sizes which are bounded by k and K. Our objective is to maximize the expected profit of the system, which is composed of the amount earned for items which pass the test (and before their patience runs out), minus costs. This is done by an appropriate choice of the decision variables, namely, the batch sizes and the number of servers at the second service station. As will be seen, even the simplest version of the batch queue, the M/M ^[k,?K]/1?+?M queue, already gives rise to serious analytical complications for any batch size larger than 1. These complications are discussed in detail, and handled for K?=?2. In view of the fact that we aim to solve realistic optimization problems for blood screening procedures, these analytical complications force us to take recourse to either a numerical approach or approximations. We present a numerical solution for the queue length distribution in the M/M ^[k,?K]/S?+?M queue and then formulate and solve several optimization problems. The power-series algorithm, which is a numerical-analytic method, is also discussed.     

Seminorms on ordered vector spaces that extend to Riesz seminorms on larger Riesz spaces

As a generalization of the notion of Riesz seminorm, a class of seminorms on directed partially ordered vector spaces is introduced, such that (1) every seminorm in the class can be extended to a Riesz seminorm on every larger Riesz space that is majorized and (2) a seminorm on an order dense linear subspace of a Riesz space is in the class if and only if it can be extended to a Riesz seminorm on the Riesz space. The latter property yields that if a directed partially ordered vector space has an appropriate Riesz completion, then a seminorm on the space is in the class if and only if it is the restriction of a Riesz seminorm on the Riesz completion. An explicit formula for the extension is given. The class of seminorms is described by means of a notion of solid unit ball in partially ordered vector spaces. Some more properties concerning restriction and extension are studied, including extension to L- and M-seminorms.     

Dominance relations in polling systems

In this paper we compare several service disciplines commonly used in polling systems. We present a sample path comparison which allows us to evaluate the efficiency of the different policies based on thetotal amount of work found in the systemat any time. The analysis is carried out for a large variety of polling schemes under fairly general conditions and can be used to construct a hierarchy of the different service schemes.     

On the calculation of vibronic coupling matrix elements

The non-diagonal matrix elements in the adiabatic Born-Oppenheimer approximation are considered. The effect of the Q-dependence of the electronic energy denominator is calculated explicitly for an arbitrary initial and final state. It is shown that the inclusion of this effect does not change the relative values of the coupling matrix elements for different initial vibronic states.