A Precoordination Complex of 1,2,3‐Trimethyl‐1,3,5‐triazacyclohexane with tert‐Butyllithium as Key Intermediate in Its Methylene Group Deprotonation

α‐Lithiated tertiary methylamines are important building blocks in all fields of chemistry, such as for the synthesis of new ligand or catalyst systems. However, the access to these compounds is still limited and the reaction mechanism, in general, not fully understood. We present herein X‐ray diffraction analyses of organolithium compounds with 1,2,3‐trimethyl‐1,3,5‐triazacyclohexane ( 1 ), such as a precoordination adduct of tert‐butyllithium, [(tBuLi)₃?C₆H₁₅N₃], which represents a potential intermediate of the lithiation of the methylene group of this ligand. By means of molecular structures and computational studies, the regioselectivity of this deprotonation reaction can be understood. Furthermore, the tBuLi adduct gives a hint to an alternative deaggregation process of organolithium compounds.     

Interactive outranking approaches for multicriteria decision-making problems with imprecise information

PROMETHEE is a powerful method, which can solve many multiple criteria decision making (MCDM) problems. It involves sophisticated preference modelling techniques but requires too much a priori precise information about parameter values (such as criterion weights and thresholds). In this paper, we consider a MCDM problem where alternatives are evaluated on several conflicting criteria, and the criterion weights and/or thresholds are imprecise or unknown to the decision maker (DM). We build robust outranking relations among the alternatives in order to help the DM to rank the alternatives and select the best alternative. We propose interactive approaches based on PROMETHEE method. We develop a decision aid tool called INTOUR, which implements the developed approaches.     

An Alternative Approach to Elliptical Motion

Elliptical rotation is the motion of a point on an ellipse through some angle about a vector. The purpose of this paper is to examine the generation of elliptical rotations and to interpret the motion of a point on an ellipsoid using elliptic inner product and elliptic vector product. To generate an elliptical rotation matrix, first we define an elliptical ortogonal matrix and an elliptical skew symmetric matrix using the associated inner product. Then we use elliptic versions of the famous Rodrigues, Cayley, and Householder methods to construct an elliptical rotation matrix. Finally, we define elliptic quaternions and generate an elliptical rotation matrix using those quaternions. Each method is proven and is provided with several numerical examples.     

The impact of socio-technical communication styles on the diversity and innovation potential of global science collaboratories

Emerging cyber-infrastructure tools are enabling scientists to transparently co-develop, share, and communicate about real-time diverse forms of knowledge artifacts. In these environments, communication preferences of scientists are posited as an important factor affecting innovation capacity and robustness of social and knowledge network structures. Scientific knowledge creation in such communities is called global participatory science (GPS). Recently, using agent-based modeling and collective action theory as a basis, a complex adaptive social communication network model (CollectiveInnoSim) is implemented. This work leverages CollectiveInnoSim implementing communication preferences of scientists. Social network metrics and knowledge production patterns are used as proxy metrics to infer innovation potential of emergent knowledge and collaboration networks. The objective is to present the underlying communication dynamics of GPS in a form of computational model and delineate the impacts of various communication preferences of scientists on innovation potential of the collaboration network. Gained insight can ultimately help policy-makers to design GPS environments and promote innovation.     

Thioflavin T: Electronic Circular Dichroism and Circularly Polarized Luminescence Induced by Amyloid Fibrils

The circularly polarized luminescence (CPL) spectrum of thioflavin T (ThT) bound to insulin amyloid fibrils has been measured for the first time. It has been found that the samples exhibiting induced circular dichroism (CD) retain the optical activity in the CPL spectra, with the same sign of the rotatory strength. The fluorescence dissymmetry factor is substantial (of the order of magnitude 10^?2). Unlike in the corresponding CD and absorption spectra, there is no shift of the CPL band with respect to the fluorescence band. It has been verified that the measured CPL spectra are free from artifacts from circularly polarized scattering of emitted light by conducting additional measurements in a medium with a refractive index similar to insulin (methylsalicylate). The CD and CPL spectra have been interpreted by means of density functional calculations carried out for ThT in its ground and first excited states in different dielectric environments and for ThT interacting with an aromatic ring. It has been found that the presence of an aromatic ring close to the ThT molecule induces Cotton effects of the same order of magnitude as the stabilization of one enantiomeric conformer. Thus, it is expected that both mechanisms contribute to the induced CD and CPL effect to a similar degree.     

Effect of chain length and charge density on the construction of polyelectrolyte multilayers on colloidal particles

Two combinations of sodium poly(4-styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) of different chain length and charge density are employed to construct multilayer films. The polyelectrolytes are assembled layer-by-layer on colloidal particles in the absence of salt. We have investigated the formation and electrical characteristics of the films by using electric light scattering technique. The results show that the film thickness is independent of the chain length when fully charged PAH (at pH 4.6) is combined with fully charged PSS. When the films are prepared with less charged PAH (at pH 6.7) and fully charged PSS, lower thickness is found for the film with shorter polymer chains. In all cases, the thickness increment realized on addition of the polymer with lower molar concentration is partially lost on exposure to the solution with higher concentration of the oppositely charged partner. When the film growth is regular (at equal molar concentrations of the fully charged polyelectrolytes), the ratio of PSS to PAH charge, estimated from the electro-optical effect values, exceeds 1. The electro-optical effect is also higher for the films ending with PSS when fully charged PSS is combined with less charged PAH (at pH 6.7). This reveals the key role of the charge in the last-adsorbed layer for the electro-optical behavior of the whole film.     

Synthesis,structural, and spectral studies of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-bis- (5-methylsalicylidene)-2,2′-diamino-4-4′-di-(trifloromethyl)-diphenyl disulfide

A new disulfide compound N,N′-bis-(5-methylsalicylidene)-2,2′-diamino-4-4′-di-(trifloromethyl)-diphenyl disulfide (C₃₀H₂₂F₆N₂O₂S₂) was prepared and characterized by ¹H-NMR, IR, mass spectroscopy, and single-crystal X-ray diffraction. Spectroscopic assignments and the crystallographic results indicate the predominance of the phenol-imine tautomeric form. [For example, N=C double bonds 1.274(9)Å and 1.275(9)Å, two very close hydrogen peaks to the atomic positions of O atoms in difference Fourier map and two strong intramolecular hydrogen bonds (O–H\(\cdots\)N) with O\(\cdots\)N distances of 2.611(10) and 2. 613(8) Åstrongly indicate that this tautomeric form is preferred]. The strong effect of the para CF₃ groups in the molecular and crystallographic arrangement was attributed to the electronegativity of the CF₃ groups.     

Solvation Effects on the Structure and Stability of Alkali Metal Carbenoids

s‐Block metal carbenoids are carbene synthons and applied in a myriad of organic transformations. They exhibit a strong structure–activity relationship, but this is only poorly understood due to the challenging high reactivity and sensitivity of these reagents. Here, we report on systematic VT and DOSY NMR studies, XRD analyses as well as DFT calculations on a sulfoximinoyl‐substituted model system to explain the pronounced solvent dependency of the carbenoid stability. While the sodium and potassium chloride carbenoids showed high stabilities independent of the solvent, the lithium carbenoid was stable at room temperature in THF but decomposed at ?10 °C in toluene. These divergent stabilities could be explained by the different structures formed in solution. In contrast to simple organolithium reagents, the monomeric THF‐solvate was found to be more stable than the dimer in toluene, since the latter more readily forms direct Li/Cl interactions which facilitate decomposition via α‐elimination.     

Reversed phase StrataTM-X resin as sorbent for automatic on-line solid phase extraction atomic absorption spectrometric determination of trace metals: comparison of polymeric-based sorbent materials

A novel on-line flow injection solid phase extraction method for the preconcentration of trace toxic metals prior determination by flame atomic absorption spectrometry (FI-SPE-FAAS) was developed. The potential application of the hydrophobic reversed phase co-polymer sorbent Strata^TM-X packed into an on-line microcolumn for the quantification of Cd(II), Pb(II), Cu(II) and Cr(VI) was demonstrated for the first time. The method was based on the on-line formation of metal complexes using sodium diethyl-dithiocarbamate (DDTC) and on the subsequent retention of them onto the sorbent material. The target analytes were completely eluted by methanol and, subsequently, directed to FAAS for quantification. All chemical and flow variables affecting the performance of the developed method were thoroughly studied and optimised. For a preconcentration time of 90 s and a sampling frequency of 28 h^?1, enhancement factors of 72, 140, 185, 63 and detection limits of 0.18, 1.6, 0.20 and 1.2 μg L ^?1 were obtained for Cd(II), Pb(II), Cu(II) and Cr(VI), respectively. The accuracy of the FI-SPE-FAAS method was evaluated by analysing certified reference materials as well as spiked environmental water samples. Furthermore, a comparative study of the analytical characteristics, the properties as well as the chemical structures of commercial polymeric based sorbent materials was employed. Strata-X sorbent was compared against Hypersep^TM SCX, Bond Elut® Plexa^TM PCX, Oasis-HLB^TM and Nobias^TM PA-1, regarding the adaptation in on-line FI-SPE-FAAS systems for metal determination, and herein presented.     

On nadir points of multiobjective integer programming problems

In this study, we consider the nadir points of multiobjective integer programming problems. We introduce new properties that restrict the possible locations of the nondominated points necessary for computing the nadir points. Based on these properties, we reduce the search space and propose an exact algorithm for finding the nadir point of multiobjective integer programming problems. We present an illustrative example on a three objective knapsack problem. We conduct computational experiments and compare the performances of two recent algorithms and the proposed algorithm.