Synthesis and complexation properties of novel triazoyl-based ferrocenyl ligands

Two new ligand derivatives of ferrocene, namely N-4-[3,5-di-(2-pyridyl)-1,2,4-triazoyl]ferrocene carbimine (L1) and N-4-[3,5-di-(2-pyridyl)-1,2,4-triazoyl]ferrocene carbamide (L2), were synthesised in good yields by reacting the known compound 3,5-di-pyridine-2-yl-[1,2,4]triazol-4-ylamine (1) with ferrocenecarbaldehyde and chlorocarbonyl ferrocene, respectively. The structures of L1 and L2 were determined by X-ray crystallography. The complexation of L1 and L2 with Cu^I, Ag^I, Zn^II and Cd^II was studied by NMR and UV-vis spectroscopies, as well as by electrochemistry, with titrations used to determine metal:ligand stoichiometries. The cyclic voltammograms of L1 and L2 and their respective complexes indicated reversible one-electron transfers corresponding to the Fc^0/+ redox couple (Fc = ferrocene), with formal electrode potentials shifting to more positive values upon metal complexation.     

多类型复发间隔时间下广义半参数风险模型

本文在多类型复发间隔时间数据下,研究了一类广义半参数风险回归模型的参数估计问题,给出了该模型中未知参数和非参数函数的一种估计方法,并证明了估计量的相合性和渐近正态性.最后利用数值模拟来评估估计量在有限样本下的表现.     

Supercritical fluid chromatography hyphenated with twin comprehensive two-dimensional gas chromatography for ultimate analysis of middle distillates

This paper reports the conditions of online hyphenation of supercritical fluid chromatography (SFC) with twin comprehensive two-dimensional gas chromatography (twin-GC × GC) for detailed characterization of middle distillates; this is essential for a better understanding of reactions involved in refining processes. In this configuration, saturated and unsaturated compounds that have been fractionated by SFC are transferred on two different GC × GC columns sets (twin-GC × GC) placed in the same GC oven. Cryogenic focusing is used for transfer of fractions into the first dimension columns before simultaneous GC × GC analysis of both saturated and unsaturated fractions. The benefits of SFC–twin-GC × GC are demonstrated for the extended alkane, iso-alkane, alkene, naphthenes and aromatics analysis (so-called PIONA analysis) of diesel samples which can be achieved in one single injection. For that purpose, saturated and unsaturated compounds have been separated by SFC using a silver loaded silica column prior to GC × GC analysis. Alkenes and naphthenes are quantitatively recovered in the unsaturated and saturated fractions, respectively, allowing their identification in various diesel samples. Thus, resolution between each class of compounds is significantly improved compared to a single GC × GC run, and for the first time, an extended PIONA analysis of diesel samples is presented.     

Convex hull: A new method to determine the separation space used and to optimize operating conditions for comprehensive two-dimensional gas chromatography

It is important to develop methods of optimizing the selection of column sets and operating conditions for comprehensive two-dimensional gas chromatography. A new method for the calculation of the percentage of separation space used was developed using Delaunay's triangulation algorithms (convex hull). This approach was compared with an existing method and showed better precision and accuracy. It was successfully applied to the selection of the most convenient column set and the geometrical parameters of second column for the analysis of 49 target compounds in wastewater.     

Quantitative assessment of moisture damage for cacao bean quality using two-dimensional gas chromatography combined with time-of-flight mass spectrometry and chemometrics

Quality control of cacao beans is a significant issue in the chocolate industry. In this report, we describe how moisture damage to cacao beans alters the volatile chemical signature of the beans in a way that can be tracked quantitatively over time. The chemical signature of the beans is monitored via sampling the headspace of the vapor above a given bean sample. Headspace vapor sampled with solid-phase micro-extraction (SPME) was detected and analyzed with comprehensive two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GC × GC–TOFMS). Cacao beans from six geographical origins (Costa Rica, Ghana, Ivory Coast, Venezuela, Ecuador, and Panama) were analyzed. Twenty-nine analytes that change in concentration levels via the time-dependent moisture damage process were measured using chemometric software. Biomarker analytes that were independent of geographical origin were found. Furthermore, prediction algorithms were used to demonstrate that moisture damage could be verified before there were visible signs of mold by analyzing subsets of the 29 analytes. Thus, a quantitative approach to quality screening related to the identification of moisture damage in the absence of visible mold is presented.     

Gaussian distribution of relaxation through human blood

The complicated structure of human blood has been characterized based on relaxation time, τ, and the Cole-Cole parameter, α, obtained from dielectric measurements. As previously reported by different authors, the experimental data show net deviation from the classical Debye model with certain distribution of relaxation times (D_τ). Plots of α versus width of the relaxation rate distribution of micro-particles inside the blood show that D_τ drastically affects the dielectric properties of the fluid. The mathematical function of D_τ is found to be Gaussian and we find that the α values of normal blood have net lower magnitude than that of diabetic blood. These results suggest that glucose in blood increases the broadness of the parameter α, which have significant importance in diabetic-biosensor manufacture.     

Modeling sequence scrambling and related phenomena in mixed-model production lines

In this paper we examine the various effects that workstations and rework loops with identical parallel processors and stochastic processing times have on the performance of a mixed-model production line. Of particular interest are issues related to sequence scrambling. In many production systems (especially those operating on just-in-time or in-line vehicle sequencing principles), the sequence of orders is selected carefully to optimize line efficiency while taking into account various line balancing and product spacing constraints. However, this sequence is often altered due to stochastic factors during production. This leads to significant economic consequences, due to either the degraded performance of the production line, or the added cost of restoring the sequence (via the use of systems such as mix banks or automated storage and retrieval systems). We develop analytical formulas to quantify both the extent of sequence scrambling caused by a station of the production line, and the effects of this scrambling on downstream performance. We also develop a detailed Markov chain model to analyze related issues regarding line stoppages and throughput. We demonstrate the usefulness of our methods on a range of illustrative numerical examples, and discuss the implications from a managerial point of view.     

A note on the gambling team method

Gerber and Li (1981) formulated, using a Markov chain embedding, a system of equations that describes relations between generating functions of waiting time distributions for occurrences of patterns in a sequence of independent repeated experiments when the initial outcomes of the process are known. We show how this system of equations can be obtained by using the classical gambling team technique. We also present a form of solution of the system and give an example showing how first results of trials influence the probabilities that a chosen pattern precedes the remaining ones in a realization of the process.     

Goal achieving probabilities of cone‐constrained mean‐variance portfolios

In this paper, we establish closed‐form formulas for key probabilistic properties of the cone‐constrained optimal mean‐variance strategy, in a continuous market model driven by a multidimensional Brownian motion and deterministic coefficients. In particular, we compute the probability to obtain to a point, during the investment horizon, where the accumulated wealth is large enough to be fully reinvested in the money market, and safely grow there to meet the investor's financial goal at terminal time. We conclude that the result of Li and Zhou [Ann. Appl. Prob., v.16, pp.1751–1763, (2006)] in the unconstrained case carries over when conic constraints are present: the former probability is lower bounded by 80% no matter the market coefficients, trading constraints, and investment goal. We also compute the expected terminal wealth given that the investor's goal is underachieved, for both the mean‐variance strategy and the aforementioned hybrid strategy where transfer to the money market occurs if it allows to safely achieve the goal. The former probabilities and expectations are also provided in the case where all risky assets held are liquidated if financial distress is encountered. These results provide investors with novel practical tools to support portfolio decision‐making and analysis. Copyright © 2013 John Wiley & Sons, Ltd.     

α-次积分半群的Trotter-kato定理

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