Target training with soft computing tools

The personal capabilities and intentions of employees indicate their performance within their organization. It is important for the organization to capture this kind of tacit knowledge since the workforce are the true experts in perceiving the organization's current reality and evaluating which assets require development – including themselves as knowledge assets. The collective inner voice of the workforce helps the organization's management to steer the company and its assets in a sustainable direction.This article presents how the collective inner voice of the workforce can be captured and how it can be used for the benefit of the organization and its employees. The objective is to support individuals’ personal aspirations, as well as to save the money, time and resources that an organization spends on personnel training.The focus of this article is on demonstrating a possible soft-computing method used for competency simulation. The process starts with a linguistic self-evaluation conducted by employees, where individuals’ own perception of current and target competence levels is captured. The self-evaluation is conducted with the help of fuzzy logic. Clusters are formed from the result dataset using an unsupervised neural network clustering method: self-organizing maps. A demonstrator tool is then used to perform a “what-if” type of analysis/simulation on the clusters in the results. With the demonstrator tool, employees can roughly test the impact of alternative training scenarios for themselves. For individuals this may open up new directions for self-development, and for organizations this may allow the efficient use of training resources. We tested the approach with a dataset from a real human resource development project among nuclear power plant operators.The case study reveals the potential of soft-computing based collective competency simulation as one part of personnel development projects in the future. Yet the techniques and the demonstrator tool used in this experiment are far from being products that employees could easily use as part of their training project. Possible benefits of the proposed approach are demonstrated in this article.     

Solid‐State Luminescence of Au?Cu?Alkynyl Complexes Induced by Metallophilicity‐Driven Aggregation

A new series of homoleptic alkynyl complexes, [{Au₂Cu₂(C₂R)₄}_n] (R=C₃H₇O ( 1 ), C₆H₁₁O ( 2 ), C₉H₁₉O ( 3 ), C₁₃H₁₁O ( 4 )), were obtained from Au(SC₄H₈)Cl, Cu(NCMe)₄PF₆, and the corresponding alkyne in the presence of a base (NEt₃). Complexes 1 – 4 aggregate upon crystallization into polymeric chains through extensive metallophilic interactions. The cluster that contains fluorenolyl functionalities, C₁₃H₉O ( 5 ), crystallizes in its molecular form as a disolvate, [Au₂Cu₂(C₂C₁₃H₉O)₄] ? 2 THF. The substitution of weakly bound THF molecules with pyridine molecules leads to the complex [Au₂Cu₂(C₂C₁₃H₉O)₄] ? 2 py ( 6 ), thus giving two polymorphs in the solid state. Such structural diversity is established through metal‐chain and hydrogen‐bond formation, which depends on the stereochemical characteristics of the organic ligands. More interestingly, this solid‐state structural arrangement affords good emission properties, such as intensity and spectroscopic profile, which are otherwise very weakly emissive in solution. Metallophilic aggregation of the {Au₂Cu₂} cluster units, as observed in the crystals, results in dramatic enhancement of the room‐temperature phosphorescence, thereby reaching a maximum quantum efficiency of 95 % ( 4 ). A theoretical approach further indicates a synergistic effect of the array of the metal chain upon aggregation, which greatly enhances the spin‐orbit coupling and, hence, the phosphorescence, thereby opening up a new direction in the field of aggregate‐enhanced emission.     

Feasibility of gas chromatography-microchip atmospheric pressure photoionization-mass spectrometry in analysis of anabolic steroids

Mass spectrometers equipped with atmospheric pressure ion sources (API-MS) have been designed to be interfaced with liquid chromatographs (LC) and have rarely been connected to gas chromatographs (GC). Recently, we introduced a heated nebulizer microchip and showed its potential to interface liquid microseparation techniques and GC with API-MS. This study demonstrates the feasibility of GC-microchip atmospheric pressure photoionization-tandem mass spectrometry (GC-μAPPI-MS/MS) in the analysis of underivatized anabolic steroids in urine. The APPI microchip provides high ionization efficiency and produces abundant protonated molecules or molecular ions with minimal fragmentation. The feasibility of GC-μAPPI-MS/MS in the analysis of six selected anabolic steroids in urine samples was studied with respect to intra-batch repeatability, linearity, linear range, and limit of detection (LOD). The method showed good sensitivity (LODs 0.2-1 ng/mL), repeatability (relative standard deviation<10%), and linearity (regression coefficient≥0.9995) and, therefore, high potential for the analysis of anabolic steroids. Quantitative performance of the method was tested with two authentic urine samples, and the results were in good agreement with those obtained with conventional GC-electron ionization-MS after derivatization.     

Separation of different ion structures in atmospheric pressure photoionization-ion mobility spectrometry-mass spectrometry (APPI-IMS-MS)

This study demonstrates how positive ion atmospheric pressure photoionization-ion mobility spectrometry-mass spectrometry (APPI-IMS-MS) can be used to produce different ionic forms of an analy te and how these can be separated. When hexane:toluene (9:1) is used as a solvent, 2,6-di-tert-butylpyridine (2,6-DtBPyr) and 2,6-di-tert-4-methylpyridine (2,6-DtB-4-MPyr) efficiently produce radical cations [M]⁺ and protonated [M + H]⁺ molecules, whereas, when the sample solvent is hexane, protonated molecules are mainly formed. Interestingly, radical cations drift slower in the drift tube than the protonated molecules. It was observed that an oxygen adduct ion, [M + O₂]⁺, which was clearly seen in the mass spectra for hexane:toluene (9:1) solutions, shares the same mobility with radical cations, [M]⁺. Therefore, the observed mobility order is most likely explained by oxygen adduct formation, i.e., the radical cation forrning a heavier adduct. For pyridine and 2-tert-butylpyridine, only protonated molecules could be efficiently formed in the conditions used. For 1- and 2-naphthol it was observed that in hexane the protonated molecule typically had a higher intensity than the radical cation, whereas in hexane:toluene (9:1) the radical cation [M]⁺ typically had a higher intensity than the protonated molecule [M + H]⁺. Interestingly, the latter drifts slower than the radical cation [M]⁺, which is the opposite of the drift pattern seen for 2,6-DtBPyr and 2,6-DtB-4-MPyr.     

The complexation of two different ammonium ions with resorcarenes in protic solvent medium investigated by electrospray ionisation Fourier transform ion cyclotron resonance mass spectrometry

The complexations of two ammonium ions (guests) with two resorcarenes (hosts) were investigated using electrospray ionisation Fourier transform ion cyclotron resonance mass spectrometry. Although the two guests and the two hosts were noticeably similar, the quantity of the corresponding supramolecular complexes formed varied significantly due to the differences in host conformations and guest ability to form non-covalent interactions.     

Insertion of noble gas atoms into cyanoacetylene: an ab initio and matrix isolation study

A computational and experimental matrix isolation study of insertion of noble gas atoms into cyanoacetylene (HCCCN) is presented. Twelve novel noble gas insertion compounds are found to be kinetically stable at the MP2 level of theory, including four molecules with argon. The first group of the computationally studied molecules belongs to noble gas hydrides (HNgCCCN and HNgCCNC), and we found their stability for Ng = Ar, Kr, and Xe. The HNgCCCN compounds with Kr and Xe have similar stability to that of previously reported HKrCN and HXeCN. The HArCCCN molecule seems to have a weaker H-Ar bond than in the previously identified HArF molecule. The HNgCCNC molecules are less stable than the HNgCCCN isomers for all noble gas atoms. The second group of the computational insertion compounds, HCCNgCN and HCCNgNC, are of a different type, and they also are kinetically stable for Ng = Ar, Kr, and Xe. Our photolysis and annealing experiments with low-temperature cyanoacetylene/Ng (Ng = Ar, Kr, and Xe) matrixes evidence the formation of two noble gas hydrides for Ng = Kr and Xe, with the strongest IR absorption bands at 1492.1 and 1624.5 cm(-1), and two additional absorption modes for each species are found. The computational spectra of HKrCCCN and HXeCCCN fit most closely the experimental data, which is the basis for our assignment. The obtained species absorb at quite similar frequencies as the known HKrCN and HXeCN molecules, which is in agreement with the theoretical predictions. No strong candidates for an Ar compound are observed in the IR absorption spectra. As an important side product of this work, the data obtained in long-term decay of KrHKr+ cations suggest a tentative assignment for the CCCN radical.     

MP2 study on adsorption of hydrated Na+ and Au+ cations on the Au(111) surface

The interactions of Na+ and Au+ cations with an Au(111) surface in the presence and absence of water molecules were investigated using Au18 and Au22 cluster models and the MP2 method with a triple-zeta valence basis set. The interactions between Na+ ions and the Au(111) surface were found to be primarily electrostatic, contrary to the much stronger Au+-Au(111) interactions that were dominated by orbital contributions. The largest CP-corrected MP2 adsorption energies were -156.9 kJ/mol for Na+ and -478.7 kJ/mol for Au+. When hydrated, Na+ prefers to be completely surrounded by water molecules rather than adsorbed to the surface, whereas Au+ remains adsorbed to the surface as water molecules bond with each other and with the Au surface. CP correction did not change the relative adsorption energy trends of Na+ or Au+ ions, but it had an effect on the interaction energy trends of the hydrated cations because of the weak water-surface and water-water interactions.     

Characterizations of Lipschitz-type,Bloch-type and Dirichlet-type spaces

Monatshefte für Mathematik - In this paper, we will give new characterizations of Lipschitz-type spaces, and establish related growth theorems for Bloch-type spaces. Then we will present...