氮氧自由基研究XVII:水溶液中哌啶氮氧自由基的电化学行为和自衰变动力学研究

循环伏安法研究表明,2,2,6,6-四甲基-4-羟基哌啶-1-氧自由基和2,2,6,6-四甲基-4-氧哌啶-1-氧自由基,在水溶液中的单电子氧化电极反应的可逆性随介质酸性,扫描速度和自由基浓度增加而增加,表明电极氧化产物可进一步发生化学反应.     

离子色谱法测定蓝藻培养液中有机酸和无机阴离子

建立了一种利用阴离子交换色谱柱分离,电导检测器同时测定17种有机酸和7种阴离子的方法。采用Ionpac AS11-HC阴离子交换柱,KOH溶液作为淋洗液,梯度洗脱,流量为1.0mL/min,柱温为30℃,进样体积为25μL。24种分析物测定结果的相对标准偏差在0.31%~2.67%之间,线性相关系数均大于0.996,平均加标回收率在80.3%~108.5%之间。该方法可用于微生物培养液中有机酸和阴离子的同时测定。     

Synthesis, structure, and electrochemical studies of molybdenum and tungsten dinitrogen, diazenido, and hydrazido complexes that contain aryl-substituted triamidoamine ligands

One-electron reduction of [ArN(3)N]MoCl complexes (Ar = C(6)H(5), 4-FC(6)H(4), 4-t-BuC(6)H(4), 3,5-Me(2)C(6)H(3)) yields complexes of the type [ArN(3)N]Mo-N=N-Mo[ArN(3)N], while two-electron reduction yields ([ArN(3)N]Mo-N=N)(-) derivatives (Ar = C(6)H(5), 4-FC(6)H(4), 4-t-BuC(6)H(4), 3,5-Me(2)C(6)H(3), 3,5-Ph(2)C(6)H(3), and 3,5-(4-t-BuC(6)H(4))(2)C(6)H(3)). Compounds that were crystallographically characterized include ([t-BuC(6)H(4)N(3)N]Mo)(2)(N(2)), Na(THF)(6)([PhN(3)N]Mo-N=N)(2)Na(THF)(3), [t-BuC(6)H(4)N(3)N]Mo-N=N-Na(15-crown-5), and ([Ph(2)C(6)H(3)N(3)N]MoNN)(2)Mg(DME)(2). Compounds of the type [ArN(3)N]Mo-N=N-Mo[ArN(3)N] do not appear to form when Ar = 3,5-Ph(2)C(6)H(3) or 3,5-(4-t-BuC(6)H(4))(2)C(6)H(3), presumably for steric reasons. Treatment of diazenido complexes (e.g., [ArN(3)N]Mo-N=N-Na(THF)(x)) with electrophiles such as Me(3)SiCl or MeOTf yielded [ArN(3)N]Mo-N=NR complexes (R = SiMe(3) or Me). These species react further to yield ([ArN(3)N]Mo-N=NMe(2))(+) species in the presence of methylating agents. Addition of anionic methyl reagents to ([ArN(3)N]Mo-N=NMe(2))(+) species yielded [ArN(3)N]Mo(N=NMe(2))(Me) complexes. Reduction of [4-t-BuC(6)H(4)N(3)N]WCl under dinitrogen leads to a rare ([t-BuC(6)H(4)N(3)N]W)(2)(N(2)) species that can be oxidized by two electrons to give a stable dication (as its BPh(4)(-) salt). Reduction of hydrazido species leads to formation of Mo=N in low yields, and only dimethylamine could be identified among the many products. Electrochemical studies revealed expected trends in oxidation and reduction potentials, but also provided evidence for stable neutral dinitrogen complexes of the type [ArN(3)N]Mo(N(2)) when Ar is a relatively bulky terphenyl substituent.     

ELECTRE: Robust ordinal regression for outranking methods

We present a new method, called ELECTRE^GKMS, which employs robust ordinal regression to construct a set of outranking models compatible with preference information. The preference information supplied by the decision maker (DM) is composed of pairwise comparisons stating the truth or falsity of the outranking relation for some real or fictitious reference alternatives. Moreover, the DM specifies some ranges of variation of comparison thresholds on considered pseudo-criteria. Using robust ordinal regression, the method builds a set of values of concordance indices, concordance thresholds, indifference, preference, and veto thresholds, for which all specified pairwise comparisons can be restored. Such sets are called compatible outranking models. Using these models, two outranking relations are defined, necessary and possible. Whether for an ordered pair of alternatives there is necessary or possible outranking depends on the truth of outranking relation for all or at least one compatible model, respectively. Distinguishing the most certain recommendation worked out by the necessary outranking, and a possible recommendation worked out by the possible outranking, ELECTRE^GKMS answers questions of robustness concern. The method is intended to be used interactively with incremental specification of pairwise comparisons, possibly with decreasing confidence levels. In this way, the necessary and possible outranking relations can be, respectively, enriched or impoverished with the growth of the number of pairwise comparisons. Furthermore, the method is able to identify troublesome pieces of preference information which are responsible for incompatibility. The necessary and possible outranking relations are to be exploited as usual outranking relations to work out recommendation in choice or ranking problems. The introduced approach is illustrated by a didactic example showing how ELECTRE^GKMS can support real-world decision problems.     

Rough set approach to multiple criteria classification with imprecise evaluations and assignments

Dominance-based Rough Set Approach (DRSA) has been introduced to deal with multiple criteria classification (also called multiple criteria sorting, or ordinal classification with monotonicity constraints), where assignments of objects may be inconsistent with respect to dominance principle. In this paper, we consider an extension of DRSA to the context of imprecise evaluations of objects on condition criteria and imprecise assignments of objects to decision classes. The imprecisions are given in the form of intervals of possible values. In order to solve the problem, we reformulate the dominance principle and introduce second-order rough approximations. The presented methodology preserves well-known properties of rough approximations, such as rough inclusion, complementarity, identity of boundaries and precisiation. Moreover, the meaning of the precisiation property is extended to the considered case. The paper presents also a way to reduce decision tables and to induce decision rules from rough approximations.     

A critical investigation of smoothed particle hydrodynamics applied to problems with free‐surfaces

In this paper, an in‐depth study of SPH method, in its original weakly compressible version, is achieved on dedicated 2D and 3D free‐surface flow test cases. These rather critical prototype problems shall constitute suitable test cases to get through when building a free‐surface SPH model. The present work aims at investigating various numerical aspects of this method, often little mentioned in literature. In particular, a great care is paid to the dynamic part of the solution, which is critical to the local hydrodynamic load prediction. The role of numerical errors in the development of acoustic frequencies in the pressure signals is discussed, as well as the influence of the choice of the sound velocity. On the shown test problems, it is also evidenced that some numerical tools are crucial to ensure the robustness and accuracy of the standard SPH method. The convergence of our model is heuristically proved on these nonlinear prototype tests, showing at the same time the very satisfactory level of accuracy reached. Through these tests, some other numerical specificities of the SPH method are discussed, such as the self‐redistribution of the particles occurring during the Lagrangian evolution. A higher order model is also proposed, and its advantages and drawbacks are discussed. Copyright © 2013 John Wiley & Sons, Ltd.     

The case of RIB at intermediate energies: Isospin effects on nuclear dynamics

In the reaction dynamics of intermediate-energy radioactive beams we can probe highly asymmetric nuclear matter in compressed as well as dilute phases. In this report some predictions are presented, based on analytical results as well as on reaction simulations. We suggest a series of experiments with RIB aimed to shed light on isospin properties of nuclear interactions in the medium. Received: 1 May 2001 / Accepted: 4 December 2001