Estimation of isotropic nuclear magnetic shieldings in the CCSD(T) and MP2 complete basis set limit using affordable correlation calculations

A linear correlation between isotropic nuclear magnetic shielding constants for seven model molecules (CH₂O, H₂O, HF, F₂, HCN, SiH₄ and H₂S) calculated with 37 methods (34 density functionals, RHF, MP2 and CCSD(T)), with affordable pcS‐2 basis set and corresponding complete basis set results, estimated from calculations with the family of polarization‐consistent pcS‐n basis sets is reported. This dependence was also supported by inspection of profiles of deviation between CBS estimated nuclear shieldings and shieldings obtained with the significantly smaller basis sets pcS‐2 and aug‐cc‐pVTZ‐J for the selected set of 37 calculation methods. It was possible to formulate a practical approach of estimating the values of isotropic nuclear magnetic shielding constants at the CCSD(T)/CBS and MP2/CBS levels from affordable CCSD(T)/pcS‐2, MP2/pcS‐2 and DFT/CBS calculations with pcS‐n basis sets. The proposed method leads to a fairly accurate estimation of nuclear magnetic shieldings and considerable saving of computational efforts. Copyright © 2013 John Wiley & Sons, Ltd.     

Competence-driven project portfolio selection,scheduling and staff assignment

This paper presents a new model for project portfolio selection, paying specific attention to competence development. The model seeks to maximize a weighted average of economic gains from projects and strategic gains from the increment of desirable competencies. As a sub-problem, scheduling and staff assignment for a candidate set of selected projects must also be optimized. We provide a nonlinear mixed-integer program formulation for the overall problem, and then propose heuristic solution techniques composed of (1) a greedy heuristic for the scheduling and staff assignment part, and (2) two (alternative) metaheuristics for the project selection part. The paper outlines experimental results on a real-world application provided by the E-Commerce Competence Center Austria and, for a slightly simplified instance, presents comparisons with the exact solution computed by CPLEX.     

Coordination Chemistry of Lipoic Acid and Related Compounds V [1]. New Heteroditopic Ligands Derived from Monoazacrown Ethers and Lipoic Acid

Summary.  Lipoyl imidazolide reacts with aza-15-crown-5 (1,4,7,10-tetraoxa-13-azacyclopentadecane) or aza-18-crown-6 (1,4,7,10,13-pentaoxa-16-azacyclooctadecane) to afford new N-lipoylated azacrown compounds in good yields. These compounds can be transformed into 1,3-dithiols and amines by reduction with complex hydrides of the disulfide and/or amide group of the lipoyl chain. The new pendant-arm macrocycles react as heteroditopic ligands by forming dithiolate and disulfide complexes with the ‘soft’ metal ions Ni²⁺ and Pd²⁺, respectively, and an amine complex with the ‘hard’ Li⁺ ion. Semiempirical and DFT calculations on the complexation of a lithium ion give a most favourable structure in which the azacrown and two solvent molecules are in contact with the metal but not the pendant arm. Received January 29, 2002; accepted (revised) March 25, 2002     

Multi-objective decision analysis for competence-oriented project portfolio selection

This paper develops a multi-objective optimization model for project portfolio selection taking employee competencies and their evolution into account. The objectives can include economic gains as well as gains expressed in terms of aggregated competence increments according to pre-defined profiles. In order to determine Pareto-optimal solutions, the overall problem is decomposed into a master problem addressing the portfolio selection itself, and a slave problem dealing with a suitable assignment of personnel to the work packages of the selected projects over time. We provide an asymptotic approximation of the problem by a linearized formulation, which allows an efficient and exact solution of the slave problem. For the solution of the master problem, we compare the multi-objective metaheuristics NSGA-II and P-ACO. Experimental results both for synthetically generated test instances and for real-world test instances, based on an application case from the E-Commerce Competence Center Austria, are presented.     

Identification of complex,naturally occurring flavonoid glycosides in kale (Brassica oleracea var. sabellica) by high‐performance liquid chromatography diode‐array detection/electrospray ionization multi‐stage mass spectrometry

Kale is a member of the Brassicaceae family and has a complex profile of flavonoid glycosides. Therefore, kale is a suitable matrix to discuss in a comprehensive study the different fragmentation patterns of flavonoid glycosides. The wide variety of glycosylation and acylation patterns determines the health‐promoting effects of these glycosides. The aim of this study is to investigate the naturally occurring flavonoids in kale. A total of 71 flavonoid glycosides of quercetin, kaempferol and isorhamnetin were identified using a high‐performance liquid chromatography diode‐array detection/electrospray ionization multi‐stage mass spectrometry (HPLC‐DAD/ESI‐MSⁿ) method. Of these 71 flavonol glycosides, 27 were non‐acylated, 30 were monoacylated and 14 were diacylated. Non‐acylated flavonol glycosides were present as mono‐, di‐, tri‐ and tetraglycosides. This is the first time that the occurrence of four different fragmentation patterns of non‐acylated flavonol triglycosides has been reported in one matrix simultaneously. In addition, 44 flavonol glycosides were acylated with p‐coumaric, caffeic, ferulic, hydroxyferulic or sinapic acid. While monoacylated glycosides existed as di‐, tri‐ and tetraglycosides, diacylated glycosides occurred as tetra‐ and pentaglycosides. To the best of our knowledge, 28 compounds in kale are reported here for the first time. These include three acylated isorhamnetin glycosides (isorhamnetin‐3‐O‐sinapoyl‐sophoroside‐7‐O‐D‐glucoside, isorhamnetin‐3‐O‐feruloyl‐sophoroside‐7‐O‐diglucoside and isorhamnetin‐3‐O‐disinapoyl‐triglucoside‐7‐O‐diglucoside) and seven non‐acylated isorhamnetin glycosides. Copyright © 2010 John Wiley & Sons, Ltd.     

A study of the exposure of various population groups to platinum in Vienna (Austria) through urine analysis by inductively coupled plasma-mass spectrometry

Platinum is emitted to environment by automobile catalytic converters (ACCs), hospitals, noble metal refineries, and other industries. Due to abrasion of ACCs platinum leaves the cars with the exhaust fumes and can thus be found in urban and rural atmospheres. To study the exposure to this element its concentration in urine is determined. Urine represents an often used specimen for monitoring studies, as it plays an important role in the elimination of various substances from the body and in addition it can be collected easily. It is supposed that the Pt-intake depends on the physical activity of a person, i.e. the amount of air inhaled and food consumed. Therefore subjects without and with one or two hip-endoprostheses were selected for this monitoring study. The medians obtained for the Pt-concentration of the urine-samples of these three groups were 3.7 µg/g, 3.3 µg/g and 1.9 µg/g for persons with no, one and two prostheses, respectively. Applying a Mann-Whitney-U-test on these data leads to a p-value of 0.051 comparing the groups with n = 0 and n = 2, and a p-value of 0.052 for n = 1 and n = 2 (n = number of prostheses).     

The influence of π-π-stacking on the light-harvesting properties of perylene bisimide antennas that are covalently linked to a [60]fullerene

A flexible organic triad consisting of two perylene bisimide antennas covalently linked to a [60]fullerene by flexible spacers has been synthesized and studied by electrochemistry, steady-state and time-resolved spectroscopy. We found that π-π-stacking of the two antenna subunits has considerable impact on the photophysics of the system and leads to a reduction of the effective light-harvesting efficiency of the assembly. This finding is important for light harvesting in flexible materials based on the dye antenna-fullerene concept.     

Public understanding of science and the perception of nanotechnology: the roles of interest in science,methodological knowledge,epistemological beliefs,and beliefs about science

In this article, we report data from an online questionnaire study with 587 respondents, representative for the adult U.S. population in terms of age, gender, and level of education. The aim of this study was to assess how interest in science and knowledge as well as beliefs about science are associated with risk and benefit perceptions of nanotechnology. The findings suggest that the U.S. public is still rather unfamiliar with nanotechnology. Those who have some knowledge mainly have gotten it from TV and the Internet. The content of current media reports is perceived as fairly positive. Knowledge of scientific methods is unrelated to benefit and risk perceptions, at least when other predictors are controlled. In contrast, positive beliefs about science (e.g., its impact on economy or health) and more sophisticated epistemological beliefs about the nature of scientific knowledge are moderately linked to more positive perceptions of nanotechnology. The only exception is the perception of scientific uncertainty: This is associated with less positive evaluations. Finally, higher engagement with science is associated with higher risk perceptions. These findings show that laypersons who are engaged with science and who are aware of the inherent uncertainty of scientific evidence might perceive nanotechnology in a somewhat more differentiated way, contrary to how it is portrayed in the media today.     

Polysulfobetaine films prepared by electrografting technique for reduction of biofouling on electroconductive surfaces

The sulfobetaine films were prepared on stainless steel and golden surfaces. In the first step, the poly(2-(dimethylamino)ethyl methacrylate) film was created by employing the electrografting polymerization technique. In the second step, this film was modified to polysulfobetaine, i.e. the polymer film bearing the zwitterionic groups. The presence of the electrografted film and its modification were determined by contact angle measurements, infrared spectroscopy in reflectance mode and X-ray photoelectron spectroscopy. The prepared films were homogeneous with the thickness from about 5 to 26 nm as determined by X-ray photoelectron spectroscopy. The atomic force microscopy measurements showed the increase of surface roughness upon the surface coating. In vitro tests using adherent RAT-2 fibroblast cells and fluorescently labelled bovine serum albumin proteins showed that prepared polysulfobetaine films can be used in applications requiring the resistance against cell attachment and biofouling.