High-resolution computer simulations of stacking of weak bases using a transient pH boundary in capillary electrophoresis. 1. Concept and impact of sample ionic strength

The dynamics of focusing weak bases using a transient pH boundary was examined via high-resolution computer simulation software. Emphasis was placed on the mechanism and impact that the presence of salt, namely, NaCl, has on the ability to focus weak bases. A series of weak bases with mobilities ranging from 5 x 10(-9) to 30 x 10(-9) m2/V x s and pKa values between 3.0 and 7.5 were examined using a combination of 65.6 mM formic acid, pH 2.85, for the separation electrolyte, and 65.6 mM formic acid, pH 8.60, for the sample matrix. Simulation data show that it is possible to focus weak bases with a pKa value similar to that of the separation electrolyte, but it is restricted to weak bases having an electrophoretic mobility of 20 x 10(-9) m2/V x s or quicker. This mobility range can be extended by the addition of NaCl, with 50 mM NaCl allowing stacking of weak bases down to a mobility of 15 x 10(-9) m2/V x s and 100 mM extending the range to 10 x 10(-9) m2/V x s. The addition of NaCl does not adversely influence focusing of more mobile bases, but does prolong the existence of the transient pH boundary. This allows analytes to migrate extensively through the capillary as a single focused band around the transient pH boundary until the boundary is dissipated. This reduces the length of capillary that is available for separation and, in extreme cases, causes multiple analytes to be detected as a single highly efficient peak.

Problems in the classical calculus of variations

This dissertation concerns convergence analysis for nonparametric problems in the calculus of variations and sufficient conditions for weak local minimizer of a functional for both nonparametric and parametric problems. Newton's method in infinite-dimensional space is proved to be well-defined and converges quadratically to a weak local minimizer of a functional subject to certain boundary conditions. Sufficient conditions for global converges are proposed and a well-defined algorithm based on those conditions is presented and proved to converge. Finite element discretization is employed to achieve an implementable line-search-based quasi-Newton algorithm and a proof of convergence of the discretization of the algorithm is included. This work also proposes sufficient conditions for weak local minimizer without using the language of conjugate points. The form of new conditions is consistent with the ones in finite-dimensional case. It is believed that the new form of sufficient conditions will lead to simpler approaches to verify an extremal as local minimizer for well-known problems in calculus of variations.

Decision-usefulness of ideal cost- and ideal value accounting for valuation and stewardship

This paper contrasts the decision-usefulness of prototype accounting regimes based on perfect accounting for value, i.e. ideal value accounting (IVA), and perfect matching of cost, i.e. ideal cost accounting (ICA). The regimes are analyzed in the context of a firm with overlapping capacity investments where projects earn excess returns and residual income is utilized as performance indicator. Provided that IVA and ICA systematically differ based on the criterion of unconditional conservatism, we assess their respective decision-usefulness for different valuation- and stewardship-scenarios. Assuming that addressees solely observe current accounting data of the firm, ICA provides information which is useful for valuation and stewardship without reservation whereas IVA entails problems under specific assumptions.

Investigating the value of privacy on online social networks: conjoint analysis

Popularity of Online Social Networks has been recently overshadowed by the privacy problems they pose. Users are getting increasingly vigilant concerning information they disclose and are strongly opposing the use of their information for commercial purposes. Nevertheless, as long as the network is offered to users for free, providers have little choice but to generate revenue through personalized advertising to remain financially viable. Our study empirically investigates the ways out of this deadlock. Using conjoint analysis we find that privacy is indeed important for users. We identify three groups of users with different utility patterns: Unconcerned Socializers, Control-conscious Socializers and Privacy-concerned. Our results provide relevant insights into how network providers can capitalize on different user preferences by specifically addressing the needs of distinct groups in the form of various premium accounts. Overall, our study is the first attempt to assess the value of privacy in monetary terms in this context.

Mixing-cell boundary conditions and apparent mass balance errors for advective-dispersive solute transport

In many field or laboratory situations, well-mixed reservoirs like, for instance, injection or detection wells and gas distribution or sampling chambers define boundaries of transport domains. Exchange of solutes or gases across such boundaries can occur through advective or diffusive processes. First we analyzed situations, where the inlet region consists of a well-mixed reservoir, in a systematic way by interpreting them in terms of injection type. Second, we discussed the mass balance errors that seem to appear in case of resident injections. Mixing cells (MC) can be coupled mathematically in different ways to a domain where advective-dispersive transport occurs: by assuming a continuous solute flux at the interface (flux injection, MC-FI), or by assuming a continuous resident concentration (resident injection). In the latter case, the flux leaving the mixing cell can be defined in two ways: either as the value when the interface is approached from the mixing-cell side (MC-RT -), or as the value when it is approached from the column side (MC-RT +). Solutions of these injection types with constant or-in one case-distance-dependent transport parameters were compared to each other as well as to a solution of a two-layer system, where the first layer was characterized by a large dispersion coefficient. These solutions differ mainly at small Peclet numbers. For most real situations, the model for resident injection MC-RI + is considered to be relevant. This type of injection was modeled with a constant or with an exponentially varying dispersion coefficient within the porous medium. A constant dispersion coefficient will be appropriate for gases because of the Eulerian nature of the usually dominating gaseous diffusion coefficient, whereas the asymptotically growing dispersion coefficient will be more appropriate for solutes due to the Lagrangian nature of mechanical dispersion, which evolves only with the fluid flow. Assuming a continuous resident concentration at the interface between a mixing cell and a column, as in case of the MC-RI + model, entails a flux discontinuity. This flux discontinuity arises inherently from the definition of a mixing cell: the mixing process is included in the balance equation, but does not appear in the description of the flux through the mixing cell. There, only convection appears because of the homogeneous concentration within the mixing cell. Thus, the solute flux through a mixing cell in close contact with a transport domain is generally underestimated. This leads to (apparent) mass balance errors, which are often reported for similar situations and erroneously used to judge the validity of such models. Finally, the mixing cell model MC-RI + defines a universal basis regarding the type of solute injection at a boundary. Depending on the mixing cell parameters, it represents, in its limits, flux as well as resident injections. (C) 1998 Elsevier Science B.V. All rights reserved.

Dementia in patients with atrial fibrillation and the value of the Hachinski ischemic score.

AIM To assess the prevalence of vascular dementia, mixed dementia and Alzheimer's disease in patients with atrial fibrillation, and to evaluate the accuracy of the Hachinski ischemic score for these subtypes of dementia. METHODS A nested case-control study was carried out. A total of 103 of 784 consecutive patients evaluated for cognitive status at the Ambulatory Geriatric Clinic had a diagnosis of atrial fibrillation. Controls without atrial fibrillation were randomly selected from the remaining 681 patients using a 1:2 matching for sex, age and education. RESULTS The prevalence of vascular dementia was twofold in patients with atrial fibrillation compared with controls (21.4% vs 10.7%, P = 0.024). Alzheimer's disease was also more frequent in the group with atrial fibrillation (12.6% vs 7.3%, P = 0.046), whereas mixed dementia had a similar distribution. The Hachinski ischemic score poorly discriminated between dementia subtypes, with misclassification rates between 46% (95% CI 28-66) and 70% (95% CI 55-83). In patients with atrial fibrillation, these rates ranged from 55% (95% CI 32-77) to 69% (95% CI 39-91%). In patients in whom the diagnosis of dementia was excluded, the Hachinski ischemic score suggested the presence of vascular dementia in 11% and mixed dementia in 30%. CONCLUSIONS Vascular dementia and Alzheimer's disease, but not mixed dementia, are more prevalent in patients with atrial fibrillation. The discriminative accuracy of the Hachinski ischemic score for dementia subtypes in atrial fibrillation is poor, with a significant proportion of misclassifications.

Don't forget asking the others! - The added value of significant other's reports on patient interpersonal style for the prediction of therapy process and outcome

Theory: Interpersonal factors play a major role in causing and maintaining depression. It is unclear, however, to what degree significant others of the patient need to be involved for characterizing the patient's interpersonal style. Therefore, our study sought to investigate how impact messages as perceived by the patients' significant others add to the prediction of psychotherapy process and outcome above and beyond routine assessments, and therapist factors. Method: 143 outpatients with major depressive disorder were treated by 24 therapists with CBT or Exposure-Based Cognitive Therapy. Interpersonal style was measured pre and post therapy with the informant‐based Impact Message Inventory (IMI), in addition to the self‐report Inventory of Interpersonal Problems (IIP‐32). Indicators for the patients' dominance and affiliation as well as interpersonal distress were calculated from these measures. Depressive and general symptomatology was assessed at pre, post, and at three months follow‐up, and by process measures after every session. Results: Whereas significant other's reports did not add significantly to the prediction of the early therapeutic alliance, central mechanisms of change, or post‐therapy outcome including therapist factors, the best predictor of outcome 3 months post therapy was an increase in dominance as perceived by significant others. Conclusions: The patients' significant others seem to provide important additional information about the patients' interpersonal style and therefore should be included in the diagnostic process. Moreover, practitioners should specifically target interpersonal change as a potential mechanism of change in psychotherapy for depression.

An MILP-based heuristic for staff scheduling problems with acceptance levels

We present a real-world staff-assignment problem that was reported to us by a provider of an online workforce scheduling software. The problem consists of assigning employees to work shifts subject to a large variety of requirements related to work laws, work shift compatibility, workload balancing, and personal preferences of employees. A target value is given for each requirement, and all possible deviations from these values are associated with acceptance levels. The objective is to minimize the total number of deviations in ascending order of the acceptance levels. We present an exact lexicographic goal programming MILP formulation and an MILP-based heuristic. The heuristic consists of two phases: in the first phase a feasible schedule is built and in the second phase parts of the schedule are iteratively re-optimized by applying an exact MILP model. A major advantage of such MILP-based approaches is the flexibility to account for additional constraints or modified planning objectives, which is important as the requirements may vary depending on the company or planning period. The applicability of the heuristic is demonstrated for a test set derived from real-world data. Our computational results indicate that the heuristic is able to devise optimal solutions to non-trivial problem instances, and outperforms the exact lexicographic goal programming formulation on medium- and large-sized problem instances.

Prognostic value of PCSK9 levels in patients with acute coronary syndromes.

AIMS Proprotein convertase subtilisin kexin 9 (PCSK9) is an emerging target for the treatment of hypercholesterolaemia, but the clinical utility of PCSK9 levels to guide treatment is unknown. We aimed to prospectively assess the prognostic value of plasma PCSK9 levels in patients with acute coronary syndromes (ACS). METHODS AND RESULTS Plasma PCSK9 levels were measured in 2030 ACS patients undergoing coronary angiography in a Swiss prospective cohort. At 1 year, the association between PCSK9 tertiles and all-cause death was assessed adjusting for the Global Registry of Acute Coronary Events (GRACE) variables, as well as the achievement of LDL cholesterol targets of <1.8 mmol/L. Patients with higher PCSK9 levels at angiography were more likely to have clinical familial hypercholesterolaemia (rate ratio, RR 1.21, 95% confidence interval, CI 1.09-1.53), be treated with lipid-lowering therapy (RR 1.46, 95% CI 1.30-1.63), present with longer time interval of chest pain (RR 1.29, 95% CI 1.09-1.53) and higher C-reactive protein levels (RR 1.22, 95% CI 1.16-1.30). PCSK9 increased 12-24 h after ACS (374 ± 149 vs. 323 ± 134 ng/mL, P < 0.001). At 1 year follow-up, HRs for upper vs. lower PCSK9-level tertiles were 1.13 (95% CI 0.69-1.85) for all-cause death and remained similar after adjustment for the GRACE score. Patients with higher PCSK9 levels were less likely to reach the recommended LDL cholesterol targets (RR 0.81, 95% CI 0.66-0.99). CONCLUSION In ACS patients, high initial PCSK9 plasma levels were associated with inflammation in the acute phase and hypercholesterolaemia, but did not predict mortality at 1 year.

hp-DGFEM for second-order mixed elliptic problems polyhedra

We prove exponential rates of convergence of hp-version discontinuous Galerkin (dG) interior penalty finite element methods for second-order elliptic problems with mixed Dirichlet-Neumann boundary conditions in axiparallel polyhedra. The dG discretizations are based on axiparallel, σ-geometric anisotropic meshes of mapped hexahedra and anisotropic polynomial degree distributions of μ-bounded variation. We consider piecewise analytic solutions which belong to a larger analytic class than those for the pure Dirichlet problem considered in [11, 12]. For such solutions, we establish the exponential convergence of a nonconforming dG interpolant given by local L 2 -projections on elements away from corners and edges, and by suitable local low-order quasi-interpolants on elements at corners and edges. Due to the appearance of non-homogeneous, weighted norms in the analytic regularity class, new arguments are introduced to bound the dG consistency errors in elements abutting on Neumann edges. The non-homogeneous norms also entail some crucial modifications of the stability and quasi-optimality proofs, as well as of the analysis for the anisotropic interpolation operators. The exponential convergence bounds for the dG interpolant constructed in this paper generalize the results of [11, 12] for the pure Dirichlet case.

SOP: Parallel surrogate global optimization with Pareto center selection for computationally expensive single objective problems

This paper presents a parallel surrogate-based global optimization method for computationally expensive objective functions that is more effective for larger numbers of processors. To reach this goal, we integrated concepts from multi-objective optimization and tabu search into, single objective, surrogate optimization. Our proposed derivative-free algorithm, called SOP, uses non-dominated sorting of points for which the expensive function has been previously evaluated. The two objectives are the expensive function value of the point and the minimum distance of the point to previously evaluated points. Based on the results of non-dominated sorting, P points from the sorted fronts are selected as centers from which many candidate points are generated by random perturbations. Based on surrogate approximation, the best candidate point is subsequently selected for expensive evaluation for each of the P centers, with simultaneous computation on P processors. Centers that previously did not generate good solutions are tabu with a given tenure. We show almost sure convergence of this algorithm under some conditions. The performance of SOP is compared with two RBF based methods. The test results show that SOP is an efficient method that can reduce time required to find a good near optimal solution. In a number of cases the efficiency of SOP is so good that SOP with 8 processors found an accurate answer in less wall-clock time than the other algorithms did with 32 processors.

Interstellar neutral helium in the heliosphere from Interstellar Boundary Explorer observations. III. Mach number of the flow, velocity vector, and temperature from the first six years of measurements

We analyzed observations of interstellar neutral helium (ISN He) obtained from the Interstellar Boundary Explorer (IBEX) satellite during its first six years of operation. We used a refined version of the ISN He simulation model, presented in the companion paper by Sokol et al. (2015b), along with a sophisticated data correlation and uncertainty system and parameter fitting method, described in the companion paper by Swaczyna et al. We analyzed the entire data set together and the yearly subsets, and found the temperature and velocity vector of ISN He in front of the heliosphere. As seen in the previous studies, the allowable parameters are highly correlated and form a four-dimensional tube in the parameter space. The inflow longitudes obtained from the yearly data subsets show a spread of similar to 6 degrees, with the other parameters varying accordingly along the parameter tube, and the minimum chi(2) value is larger than expected. We found, however, that the Mach number of the ISN He flow shows very little scatter and is thus very tightly constrained. It is in excellent agreement with the original analysis of ISN He observations from IBEX and recent reanalyses of observations from Ulysses. We identify a possible inaccuracy in the Warm Breeze parameters as the likely cause of the scatter in the ISN He parameters obtained from the yearly subsets, and we suppose that another component may exist in the signal or a process that is not accounted for in the current physical model of ISN He in front of the heliosphere. From our analysis, the inflow velocity vector, temperature, and Mach number of the flow are equal to lambda(ISNHe) = 255 degrees.8 +/- 0 degrees.5, beta(ISNHe) = 5 degrees.16 +/- 0 degrees.10, T-ISNHe = 7440 +/- 260 K, nu(SNHe) = 25.8 +/- 0.4 km s(-1), and M-ISNHe = 5.079 +/- 0.028, with uncertainties strongly correlated along the parameter tube.

Determination of sulfite and manganese in sediments from the K/T boundary

The solid-state-physics technique of electron spin resonance (ESR) has been employed in an exploratory study of marine limestones and impact-related deposits from Cretaceous-Tertiary (KT) boundary sites including Spain (Sopelana and Caravaca), New Jersey (Bass River), the U.S. Atlantic continental margin (Blake Nose, ODP Leg 171B/1049/A), and several locations in Belize and southern Mexico within -600 km of the Chicxulub crater. The ESR spectra of SO3(1-) (a radiation-induced point defect involving a sulfite ion substitutional for CO3(2-) which has trapped a positive charge) and Mn(2+) in calcite were singled out for analysis because they are unambiguously interpretable and relatively easy to record. ESR signal strengths of calcite-related SO3(1-) and Mn(2+) have been studied as functions of stratigraphic position in whole-rock samples across the KT boundary at Sopelana, Caravaca, and Blake Nose. At all three of these sites, anomalies in SO3(1-) and/or Mn(2+) intensities are noted at the KT boundary relative to the corresponding background levels in the rocks above and below. At Caravaca, the SO3(1-) background itself is found to be lower by a factor of 2.7 in the first 30,000 years of the Tertiary relative to its steady-state value in the last 15,000 years of the Cretaceous, indicating either an abrupt and quasi-permanent change in ocean chemistry (or temperature) or extinction of the marine biota primarily responsible for fixing sulfite in the late Cretaceous limestones. An exponential decrease in the Mn(2+) concentration per unit mass calcite, [Mn(2+)], as the KT boundary at Caravaca is approached from below (1/e characteristic length =1.4 cm) is interpreted as a result of post-impact leaching of the seafloor. Absolute ESR quantitative analyses of proximal impact deposits from Belize and southern Mexico group naturally into three distinct fields in a twodimensional [SO3(1-)]-versus-[Mn(2+)] scatter plot. These fields contain (I) limestone ejecta clasts, (II) accretionary lapilli, and (III) a variety of SO3(1-) -depleted/Mn(2+) enriched impact deposits. Data for the investigated non-impact-related Cretaceous and Tertiary marine limestones (Spain and Blake Nose) fall outside of these three fields. With reference to thes enon-impact deposits, fields I, II, and III can be respectively characterized as Mn(2+) -depleted, SO3(1-) -enhanced, and SO3(1-) -depleted. It is proposed that (1) field I represents calcites from the Yucatin Platform, and that the Mn(2+) -depleted signature can be used as an indicator of primary Chicxulub ejecta in deep marine environments and (2) field II represents calcites that include a component formed in the vapor plume, either from condensation in the presence of CO2/SO3(1-) -rich vapors, or reactions between CaO and CO2/SO3 rich vapors, and that this SO3(1-) -enhanced signature can be used as an indicator of impact vapor plume deposits. Given these two propositions, the ESR data for the Blake Nose deposits are ascribed to the presence of basal coarse calcitic Chicxulub ejecta clasts, while the finer components that are increasingly represented toward the top are interpreted to contain high- SO3(1-) calcite from the vapor plume. The apparently-undisturbed Bass River deposit may contain even higher concentrations of vapor-plume calcite. None of the three components included in field III appear to be represented at distal, deep marine KT-boundary sites; this field may include several types of impact-related deposits of diverse origins and diagenetic histories.

Stratigraphy of the Campanian-Maastrichtian boundary in ODP Hole 122-762C

An integrated framework of magnetostratigraphy, calcareous microfossil bio-events, cyclostratigraphy and d13C stratigraphy is established for the upper Campanian-Maastrichtian of ODP Hole 762C (Exmouth Plateau, Northwestern Australian margin). Bulk-carbonate d13C events and nannofossil bio-events have been recorded and plotted against magnetostratigraphy, and provided absolute ages using the results of the cyclostratigraphic study and the recent astronomical calibration of the Maastrichtian. Thirteen carbon-isotope events and 40 nannofossil bio-events are recognized and calibrated with cyclostratigraphy, as well as 14 previously published foraminifer events, thus constituting a solid basis for large-scale correlations. Results show that this site is characterized by a nearly continuous sedimentation from the upper Campanian to the K-Pg boundary, except for a 500 kyr gap in magnetochron C31n. Correlation of the age-calibrated d13C profile of ODP Hole 762C to the d13C profile of the Tercis les Bains section, Global Stratotype Section and Point of the Campanian-Maastrichtian boundary (CMB), allowed a precise recognition and dating of this stage boundary at 72.15 ± 0.05 Ma. This accounts for a total duration of 6.15 ± 0.05 Ma for the Maastrichtian stage. Correlation of the boundary level with northwest Germany shows that the CMB as defined at the GSSP is ~800 kyr younger than the CMB as defined by Belemnite zonation in the Boreal realm. ODP Hole 762C is the first section to bear at the same time an excellent recovery of sediments throughout the upper Campanian-Maastrichtian, a precise and well-defined magnetostratigraphy, a high-resolution record of carbon isotope events and calcareous plankton biostratigraphy, and a cyclostratigraphic study tied to the La2010a astronomical solution. This section is thus proposed as an excellent reference for the upper Campanian-Maastrichtian in the Indian Ocean.