Surface modification of thermally expandable microspheres by grafting poly(glycidyl methacrylate) using ARGET ATRP

This study demonstrates the surface modification of thermally expandable core/shell microspheres by grafting glycidyl methacrylate (GMA) using activators regenerated by electron transfer (ARGET) ATRP. To retain the expansion properties it was essential to minimize the shear forces, use solvents compatible with the microspheres and keep the reaction times short (three hours or less). Using microspheres with hydroxyl groups on the surface, it was found that after converting these to α-bromo esters, GMA could be grafted by ARGET ATRP using only 50 ppm of copper catalyst in toluene at 30 °C. Decent control of the polymerization was achieved with PMDETA as ligand reaching PDIs of 1.4 for the solution polymerization of GMA. When microspheres were present, the polymerization was less controlled with higher PDIs. The epoxide groups of the grafted microspheres were hydrolyzed by HCl in THF providing a hydrophilic surface of the microsphere. The expansion property of the microspheres was studied after each reaction step by thermal mechanical analysis, and it was found that the expansion capacity was well preserved with only limited negative effect on the microspheres.     

Chemometric deconvolution of gas chromatographic unresolved conjugated linoleic acid isomers triplet in milk samples

A generally known problem of GC separation of trans-7;cis-9; cis-9,trans-11; and trans-8,cis-10 CLA (conjugated linoleic acid) isomers was studied by GC–MS on 100 m capillary column coated with cyanopropyl silicone phase at isothermal column temperatures in a range of 140–170 °C. The resolution of these CLA isomers obtained at given conditions was not high enough for direct quantitative analysis, but it was, however, sufficient for the determination of their peak areas by commercial deconvolution software. Resolution factors of overlapped CLA isomers determined by the separation of a model CLA mixture prepared by mixing of a commercial CLA mixture and CLA isomer fraction obtained by the HPLC semi-preparative separation of milk fatty acids methyl esters were used to validate the deconvolution procedure. Developed deconvolution procedure allowed the determination of the content of studied CLA isomers in ewes’ and cows’ milk samples, where dominant isomer cis-9,trans-11 is eluted between two small isomers trans-7,cis-9 and trans-8,cis-10 (in the ratio up to 1:100).     

Zinc azaphthalocyanines with pyridin-3-yloxy peripheral substituents

Phthalocyanines (Pc), which are peripherally substituted with pyridin-3-yloxy groups, have shown promise as sensitizers for photodynamic cancer therapy (PDT). Some aza-analogues (AzaPc) are reported here. Four monomers were synthesized, i.e. 5,6-di(pyridin-3-yloxy)pyrazine-2,3-dicarbonitrile, and three pyrazine-2,3-dicarbonitriles, substituted with pyridin-3-yloxy- in combination with H, Me and Ph groups. Cyclotetramerizations of these monomers with the reagent Zn(quinoline)₂Cl₂ yielded the targeted ZnAzaPcs in 20–40% yields.The cyclotetramerizations were accompanied, and apparently initiated, by complexation between zinc(II) and the pyridin-3-yloxy groups attached to the pyrazine-dicarbonitriles. Two such zinc(II) complexes were isolated and characterized. Identifications of all new substances were primarily based on NMR spectra, where the pulse techniques COSY, NOESY, HSQC and HMBC were applied. Molecular ions of the ZnAzaPcs were determined by mass spectrometry (MALDI-TOF). The UV–Vis spectra of these macrocycles were as expected, with Q-band absorptions at 630–650 nm and molar extinction coefficients, ε, 70 000–100 000. Eight peripheral pyridin-3-yloxy groups induced a small blue shift of the Q-band, from 636 nm for unsubstituted ZnAzaPc, to 630 nm, whereas a red shifted Q-band at 650 nm resulted from the combination of phenyl and pyridin-3-yloxy substituents. Improved solubilities were observed for the unsymmetrical ZnAzaPcs compared to octa(pyridin-3-yloxy)ZnAzaPc.     

Structural and Magnetic Insights into the Trinuclear Ferrocenophane and Unexpected Hydrido Inverse Crown Products of Alkali‐Metal‐Mediated Manganation(II) of Ferrocene

With the aim of introducing the diisopropylamide [NiPr₂] ^? ligand to alkali‐metal‐mediated manganation (AMMMn) chemistry, the temperature‐dependent reactions of a 1:1:3 mixture of butylsodium, bis(trimethylsilylmethyl)manganese(II), and diisopropylamine with ferrocene in hexane/toluene have been investigated. Performed at reflux temperature, the reaction affords the surprising, ferrocene‐free, hydrido product [Na₂Mn₂ (μ‐H)₂{N(iPr)₂}₄]?2 toluene ( 1 ), the first Mn hydrido inverse crown complex. Repeating the reaction rationally, excluding ferrocene, produces 1 in an isolated crystalline yield of 62 %. At lower temperatures, the same bimetallic amide mixture leads to the manganation of ferrocene to generate the first trimanganese, trinuclear ferrocenophane, [{Fe(C₅H₄)₂}₃{Mn₃Na₂(NiPr₂)₂ (HNiPr₂)₂}] ( 2 ) in an isolated crystalline yield of 81 %. Both 1 and 2 have been characterised by X‐ray crystallographic studies. The magnetic properties of paramagnetic 1 and 2 have also been examined by variable‐temperature magnetisation measurements on powdered samples. For 1 , the room‐temperature value for χT is 3.45 cm³ K mol^?1, and on lowering the temperature a strong antiferromagnetic coupling between the two Mn ions is observed. For 2 , the room‐temperature value for χT is 4.06 cm³ K mol^?1, which is significantly lower than the expected value for three isolated paramagnetic Mn^II ions.     

Structurally Defined Potassium‐Mediated Zincation of Pyridine and 4‐R‐Substituted Pyridines (R=Et,iPr, tBu,Ph, and Me2N) by Using Dialkyl–TMP–Zincate Bases

Two potassium–dialkyl–TMP–zincate bases [(pmdeta)K(μ‐Et)(μ‐tmp)Zn(Et)] ( 1 ) (PMDETA=N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine, TMP=2,2,6,6‐tetramethylpiperidide), and [(pmdeta)K(μ‐nBu)(μ‐tmp)Zn(nBu)] ( 2 ), have been synthesized by a simple co‐complexation procedure. Treatment of 1 with a series of substituted 4‐R‐pyridines (R=Me₂N, H, Et, iPr, tBu, and Ph) gave 2‐zincated products of the general formula [{2‐Zn(Et)₂‐μ‐4‐R‐C₅H₃N}₂ ? 2{K(pmdeta)}] ( 3 – 8 , respectively) in isolated crystalline yields of 53, 16, 7, 23, 67, and 51 %, respectively; the treatment of 2 with 4‐tBu‐pyridine gave [{2‐Zn(nBu)₂‐μ‐4‐tBu‐C₅H₃N}₂ ? 2{K(pmdeta)}] ( 9 ) in an isolated crystalline yield of 58 %. Single‐crystal X‐ray crystallographic and NMR spectroscopic characterization of 3 – 9 revealed a novel structural motif consisting of a dianionic dihydroanthracene‐like tricyclic ring system with a central diazadicarbadizinca (ZnCN)₂ ring, face‐capped on either side by PMDETA‐wrapped K⁺ cations. All the new metalated pyridine complexes share this dimeric arrangement. As determined by NMR spectroscopic investigations of the reaction filtrates, those solutions producing 3 , 7 , 8 , and 9 appear to be essentially clean reactions, in contrast to those producing 4 , 5 , and 6 , which also contain laterally zincated coproducts. In all of these metalation reactions, the potassium–zincate base acts as an amido transfer agent with a subsequent ligand‐exchange mechanism (amido replacing alkyl) inhibited by the coordinative saturation, and thus, low Lewis acidity of the 4‐coordinate Zn centers in these dimeric molecules. Studies on analogous trialkyl–zincate reagents in the absence and presence of stoichiometric or substoichiometric amounts of TMP(H) established the importance of Zn? N bonds for efficient zincation.     

Cooperative metaheuristics for the permutation flowshop scheduling problem

In this work, we propose cooperative metaheuristic methods for the permutation flowshop scheduling problem considering two objectives separately: total tardiness and makespan. We use the island model where each island runs an instance of the algorithm and communications start when the islands have reached certain level of evolution, that is, communication is not allowed from the beginning of the execution. Subsequent ones occur when new better solutions are found. We carry out an exhaustive comparison of the cooperative methods against the sequential counterparts running in completely comparable scenarios. Results have been carefully analysed by means of statistical procedures and we can conclude that the cooperative methods yield much better results than the sequential algorithms and state-of-the-art methods running in the same number of processors but without communications. The proposed cooperative schemes are easy to apply to other algorithms and problems.     

Relating the perspectives of the balanced scorecard for R&D by means of DEA

The objective of this article is to propose a framework for analysis of the relationships between the four perspectives of the balanced scorecard (BSC) of Kaplan and Norton. To this end, several different models of efficiency have been developed, utilising data envelopment analysis (DEA). Each of the variables has been extracted from a model of the BSC for research and development (R&D) activities. A study has been carried out with 90 companies to illustrate a case of this analysis.     

Determination of polymer additives by liquid chromatography coupled with mass spectrometry. A comparison of atmospheric pressure photoionization (APPI), atmospheric pressure chemical ionization (APCI), and electrospray ionization (ESI)

A method for the determination of polymer additives like antioxidants, UV absorbers and processing stabilizers using liquid chromatography (LC) coupled with atmospheric pressure photoionization mass spectrometry (APPI-MS) is presented. Ion source parameters were optimized regarding temperatures, gas flow rates, and voltages applied. Detection limits were determined using APPI with or without dopant and were compared with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). Differences between APPI, ESI and APCI are pointed out and the effect of the dopant toluene and acetone is discussed. The optimized method yielded detection limits between 0.001 mg L⁻¹ and 0.022 mg L⁻¹ for 15 different analytes. Linear calibration plots could be obtained for all solutes over a wide concentration range showing satisfying repeatability with standard deviations of peak areas between 3.4% and 7.6%. The results indicate that the developed method can be regarded as suitable for the quantitative determination of polymer additives even at low concentration levels.     

Verifying genuine high-order entanglement

High-order entanglement embedded in multipartite multilevel quantum systems (qudits) with many degrees of freedom (DOFs) plays an important role in quantum foundation and quantum engineering. Verifying high-order entanglement without the restriction of system complexity is a critical need in any experiments on general entanglement. Here, we introduce a scheme to efficiently detect genuine high-order entanglement, such as states close to genuine qudit Bell, Greenberger-Horne-Zeilinger, and cluster states as well as multilevel multi-DOF hyperentanglement. All of them can be identified with two local measurement settings per DOF regardless of the qudit or DOF number. The proposed verifications together with further utilities such as fidelity estimation could pave the way for experiments by reducing dramatically the measurement overhead.     

Chiral separation of cathinone derivatives using β‐cyclodextrin‐assisted capillary electrophoresis–Comparison of four different β‐cyclodextrin derivatives used as chiral selectors

In the past decade, more than 100 different cathinone derivatives slopped over entire Europe due to their enormous popularity. Generally, these novel psychoactive substances are easily available via the internet. This fact leads to various social problems, since cathinones are substances with consciousness‐changing effects and are mainly misused for recreational matters by their consumers. Cathinones possess a chiral center including two enantiomeric forms with potentially different pharmacological behavior. This fact makes analytical method development regarding their chiral separation indispensable. In this study, a chiral capillary zone electrophoresis method for the enantioseparation of 61 cathinone and pyrovalerone derivatives was developed by means of four different β‐cyclodextrin derivatives. As chiral selectors, native β‐cyclodextrin as well as three of its derivatives namely acetyl‐β‐cyclodextrin, 2‐hydroxypropyl‐β‐cyclodextrin, and carboxymethyl‐β‐cyclodextrin were used. The cathinone and pyrovalerone derivatives were either purchased in internet stores or seized by police. As a result, overall 58 of 61 studied substances were partially or baseline separated by at least one of the four chiral selectors using 10 mM of β‐cyclodextrin derivative in a 10 mM sodium phosphate buffer (pH 2.5). Furthermore, the method was found to be suitable for simultaneous enantioseparations, for enantiomeric purity checks and to differentiate between positional isomers. Moreover, an intra‐ and an interday validation was performed successfully for each chiral selector to prove the robustness of the method.