Assessment of accuracy and precision in speciation analysis by competitive ligand equilibration-cathodic stripping voltammetry (CLE-CSV) and application to Antarctic samples

The analytical performances of Competitive Ligand Equilibration with Cathodic Stripping Voltammetric detection of the labile fraction (CLE-CSV) were assessed. This speciation method enables the concentration of natural ligand(s) and their conditional stability constants for the complexation of the investigated metal to be determined through thermodynamic considerations.Literature data were discussed and general trends in the precision of the determined parameters identified: ligand concentrations were affected, on average, by a 10% relative percentage standard deviation (RSD%), whereas conditional stability constants showed much lower precision, with an average RSD% of 50%.New experimental data were collected to obtain a complete assessment of accuracy and precision attainable for the determination of strong ligands at the ultra trace level, enabling the whole protocol to be evaluated. Firstly, the side reaction coefficient alpha for the formation of the complex between the added ligand and the investigated metal (α_CuL) was determined. The method was subsequently applied to the analysis of solution containing ligand at trace levels (5-50 nM) with known complexing characteristics. Copper was used as the model metal ion and ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) as the model ligands. Results evidenced that the CLE-CSV protocol is not affected by systematic errors in the determination of both ligand concentration and the conditional stability constants. Good precision is obtained for ligand concentrations, with an average relative standard deviation (RSD%) of 5%; an average RSD% of 23% was calculated for the conditional stability constants. Including the contribution of the uncertainty in the value of α_CuL in the evaluation of the uncertainty in the latter parameter increased the RSD% up to 40%. The CLE-CSV protocol was subsequently applied to the detection of strong ligands in water samples collected in Antarctica: precision was shown to be comparable with literature data.     

“Bricks vs. Clicks”: The impact of manufacturer encroachment with a dealer leasing and selling of durable goods

In durable goods markets, many brand name manufacturers, including IBM, HP, Epson, and Lenovo, have adopted dual-channel supply chains to market their products. There is scant literature, however, addressing the product durability and its impact on players’ optimal strategies in a dual-channel supply chain. To fill this void, we consider a two-period dual-channel model in which a manufacturer sells a durable product directly through both a manufacturer-owned e-channel and an independent dealer who adopts a mix of selling and leasing to consumers. Our results show that the manufacturer begins encroaching into the market in Period 1, but the dealer starts withdrawing from the retail channel in Period 2. Moreover, as the direct selling cost decreases, the equilibrium quantities and wholesale prices become quite angular and often nonmonotonic. Among other results, we find that both the dealer and the supply chain may benefit from the manufacturer’s encroachment. Our results also indicate that both the market structure and the nature of competition have an important impact on the player’s (dealer’s) optimal choice of leasing and selling.     

A new methodology for generating and combining statistical forecasting models to enhance competitive event prediction

Forecasting methods are routinely employed to predict the outcome of competitive events (CEs) and to shed light on the factors that influence participants’ winning prospects (e.g., in sports events, political elections). Combining statistical models’ forecasts, shown to be highly successful in other settings, has been neglected in CE prediction. Two particular difficulties arise when developing model-based composite forecasts of CE outcomes: the intensity of rivalry among contestants, and the strength/diversity trade-off among individual models. To overcome these challenges we propose a range of surrogate measures of event outcome to construct a heterogeneous set of base forecasts. To effectively extract the complementary information concealed within these predictions, we develop a novel pooling mechanism which accounts for competition among contestants: a stacking paradigm integrating conditional logit regression and log-likelihood-ratio-based forecast selection. Empirical results using data related to horseracing events demonstrate that: (i) base model strength and diversity are important when combining model-based predictions for CEs; (ii) average-based pooling, commonly employed elsewhere, may not be appropriate for CEs (because average-based pooling exclusively focuses on strength); and (iii) the proposed stacking ensemble provides statistically and economically accurate forecasts. These results have important implications for regulators of betting markets associated with CEs and in particular for the accurate assessment of market efficiency.     

Synchronization control for the competitive complex networks with time delay and stochastic effects

The synchronization control problem for the competitive complex network with time delay and stochastic effects is investigated by using the stochastic technique and Lyapunov stability theory. The competitive complex network means that the dynamical varying rate of a part of nodes is faster than other nodes. Some synchronization criteria are derived by the full controller and pinning controller, respectively, and these criteria are convenient to be used for concision. A numerical example is provided to illustrate the effectiveness of the method proposed in this paper.     

Single and binary adsorption of proteins on ion-exchange adsorbent: The effectiveness of isothermal models

Simultaneous and sequential adsorption equilibria of single and binary adsorption of bovine serum albumin and bovine hemoglobin on Q Sepharose FF were investigated in different buffer constituents and initial conditions. The results in simultaneous adsorption showed that both proteins underwent competitive adsorption onto the adsorbent following greatly by protein-surface interaction. Preferentially adsorbed albumin complied with the universal rule of ion-exchange adsorption whereas buffer had no marked influence on hemoglobin adsorption. Moreover, an increase in initial ratios of proteins was benefit to a growth of adsorption density. In sequential adsorption, hemoglobin had the same adsorption densities as single-component adsorption. It was attributed to the displacement of preadsorbed albumin and multiple layer adsorption of hemoglobin. Three isothermal models (i.e. extended Langmuir, steric mass-action, and statistical thermodynamic (ST) models) were introduced to describe the ion-exchange adsorption of albumin and hemoglobin mixtures. The results suggested that extended Langmuir model gave the lowest deviation in describing preferential adsorption of albumin at a given salt concentration while steric mass-action model could very well describe the salt effect in albumin adsorption. For weaker adsorbed hemoglobin, ST model was the preferred choice. In concert with breakthrough data, the research further revealed the complexity in ion-exchange adsorption of proteins.     

Scheduling with step-improving processing times

We consider the scheduling problem of minimizing the makespan on a single machine with step-improving job processing times around a common critical date. For this problem we give an NP-hardness proof, a fast pseudo-polynomial time algorithm, an FPTAS, and an on-line algorithm with best possible competitive ratio.     

Competitive facility location and design problem

We develop a spatial interaction model that seeks to simultaneously optimize location and design decisions for a set of new facilities. The facilities compete for customer demand with pre-existing competitive facilities and with each other. The customer demand is assumed to be elastic, expanding as the utility of the service offered by the facilities increases. Increases in the utility can be achieved by increasing the number of facilities, design improvements, or locating facilities closer to the customer.     

Liquid-phase hydrogenation of methyl oleate on a Ni/α-Al2O3 catalyst: A study based on kinetic models describing extreme and intermediate adsorption regimes

The kinetics of the hydrogenation of methyl oleate on a Ni/α-Al₂O₃ catalyst was studied in the absence of mass-transport limitation, at 398 ≤ T ≤ 443 K and 3.7 ≤ P_H2 ≤ 6.5 bar. The kinetic modeling was performed on the basis of elementary step mechanisms involving different regimes of competition between hydrogen and methyl oleate. Admitting a distinction between occupied-sites and covered-sites by the large molecule of methyl oleate, a rigorous proposal was made to link the seemingly separate kinetic models corresponding to the extreme modes of competitive and non-competitive adsorption, without having to draw the common distinction between two types of surface sites. General rate equations were formulated without expressing opinion a priori on whether the adsorption regime is competitive or non-competitive. Then, typical LHHW rate equations for both extreme adsorption regimes were straightforwardly derived as special cases. Statistical results demonstrated the inadequacy of the models approaching non-competitive adsorption to describe the experimental data but results did not allow a definite discrimination between rival models with competitive and semi-competitive adsorption. A mechanistic model featuring dissociative adsorption of hydrogen, molecule of methyl oleate interacting with a single atom of Ni, and second insertion of hydrogen as RDS, proved to be the best candidate to describe the experimental data satisfactorily with physically reasonable parameters. As a distinctive feature, the model considering semi-competitive adsorption gave additional indication that the adsorbed molecule of methyl oleate could cover up to seven surface sites. From this finding, the semi-competitive model seems to be more realistic than the competitive one.     

Online scheduling with machine cost and rejection

In this paper we define and investigate a new scheduling model. In this new model the number of machines is not fixed; the algorithm has to purchase the used machines, moreover the jobs can be rejected. We show that the simple combinations of the algorithms used in the area of scheduling with rejections and the area of scheduling with machine cost are not constant competitive. We present a 2.618-competitive algorithm called OPTCOPY.     

竞争型的n元风险模型

保险市场中存在激烈的竞争,针对这种情形提出竞争型的n元风险模型,定义了两种破产时间,利用经典风险模型已有结论和条件期望的性质,得到相应的有限时间破产概率和最终破产概率表达式,以及每个保险公司有限时间破产概率和最终破产概率.