Interpretation of TOF-SIMS data based on information entropy of spectra

Time-of-flight secondary ion mass spectrometry (TOF-SIMS), when used for the analysis of complex material samples, typically provides data that are complicated and challenging to understand. Therefore, additional data analysis techniques, such as multivariate analysis, are often required to facilitate the interpretation of TOF-SIMS data. In this study, a new method based on the information entropy (Shannon entropy) is proposed as an indicator of the outline characteristics of an unknown sample, such as changes in the material within the sample and mixing conditions. The Shannon entropy values are calculated using the relative intensity of every secondary ion normalized to the total ion count and reflect the diversity of secondary ions in the spectrum. Mixed samples containing two organic electroluminescence materials of different ratios, multilayers of Irganox 1010, and other organic materials were employed to evaluate the utility of Shannon entropy in the analysis of TOF-SIMS data. The findings demonstrate that the Shannon entropy of a spectrum indicates differences in materials and changes in the conditions of a material in a sample without the need for peak identification or the knowledge of specific peaks corresponding to the materials in the sample.     

Garcinielliptone G from Garcinia subelliptica Induces Apoptosis in Acute Leukemia Cells

Cytotoxicity and apoptosis-inducing properties of compounds isolated from Garcinia subelliptica leaves were investigated. The hexane-soluble portion of MeOH extracts of G. subelliptica leaves that showed cytotoxic activity was separated to yield seven compounds 1–7. Chemical structure analysis using NMR spectroscopy and mass spectrometry confirmed that compound 1 was canophyllol, and compounds 2–7 were garcinielliptones N, O, J, G, F, and garcinielliptin oxide, respectively. Among them, garcinielliptone G (5) showed growth inhibition by causing apoptosis in THP-1 and Jurkat cells derived from human acute monocytic leukemia and T lymphocyte cells, respectively. Apoptosis induced by garcinielliptone G (5) was demonstrated by the detection of early apoptotic cells with fluorescein-labeled Annexin V and increases in cleaved caspase-3 and cleaved PARP protein levels. However, the addition of caspase inhibitor Z-VAD-FMK did not affect growth arrest or apoptosis induction. These results suggest that garcinielliptone G (5) can induce both caspase-3 activation and caspase-independent apoptosis. Therefore, garcinielliptone G (5) may be a potential candidate for acute leukemia treatment.     

Development of a certified reference material for the determination of perfluorooctanoic acid

A certified reference material (CRM) for the determination of perfluorooctanoic acid (PFOA) has been issued as NMIJ CRM 4056-a by the National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). Purity (kg kg^?1) based on a titration method was determined by subtracting the mass fractions of impurities measured using liquid chromatography/mass spectrometry (LC/MS) from those of acids expressed as PFOA measured by a neutralization potentiometric titration. To validate an obtained result, purity based on a mass balance method was determined by subtracting the mass fractions of impurities, measured using LC/MS, Karl-Fischer titration (KFT), and vacuum evaporation, from 1 kg kg^?1. Results from both titration and mass balance methods were in agreement within the accepted limits of uncertainty. The certified purity of NMIJ CRM 4056-a was determined to be 0.959 kg kg^?1, calculated as the mean of the results obtained with the two methods. The standard uncertainty of the certified purity was evaluated from purity evaluations as well as from sample homogeneity and stability obtained from LC/MS and KFT analyses. Consequently, the expanded uncertainty was estimated to be 0.005 kg kg^?1 with a coverage factor of k = 2.     

Supramolecular polymer gels from polystyrene bearing cyclic amidine Group and acrylic acid/n‐butyl acrylate copolymers

We have prepared supramolecular polymer gels by mixing solutions of a polystyrene bearing cyclic amidine pendant groups (Poly‐A) and copolymers of acrylic acid and n‐butyl acrylate (Poly‐C), followed by evaporation. FT‐IR analysis indicated that the gels were formed through three‐dimensional network of the amidinium‐carboxylate salt bridge. DSC study showed that the Poly‐A and the Poly‐C were miscible when the salt bridge content was high. On the other hand, the mixtures with small salt bridge content showed phase separation. Dynamic shear measurements showed that the gel prepared from Poly‐A and Poly‐C with acrylic acid unit content of 15% had G' higher than G″ over a temperature range of ?22 °C to 32 °C, in which the G' value reached almost 1 MPa. The gel had a crossover point of G' and G″ at 32 °C, very close to room temperature, which suggested facile processability. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 765–770     

Spectroscopic and crystallographic studies on the stability of self-assembled coordination nanotubes

On complexation with (en)Pd(NO3)2, tetrakis(3,5-pyridine) ligand gives two isomeric coordination nanotubes, which are in slow equilibrium despite the presence of sixteen Pd-N bonds in the tube framework.     

Comonomer-unit compositions, physical properties and biodegradability of bacterial copolyhydroxyalkanoates

The comonomer-unit compositions and their distribution of as-produced bacterial copolyesters, including poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxy-butyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and poly(3-hydroxybutyrate-co-4-hydroxybutyrate) are described in this paper. Each copolyester sample can be comonomer-unit compositionally fractionated into several fractions, indicating that the original copolymers are mixtures of copolymers with different comonomer-unit compositions. The effects of comonomer-unit compositional distribution on thermal properties, crystallization, biodegradability and solid-state phase behavior are investigated using comonomer compositionally fractionated copolymers.     

Optical probing of spin polarization of electrons in quantum dot edge channels

We propose an optical method for the investigation of the quantum dot edge channels by utilizing circularly polarized photoluminescence in the integer-quantum-Hall-effect regime. One of the advantages of our method is that the degree of the spin-polarization of the electrons in the inner- and outer-compressible liquids can be probed separately. The observed polarized photoluminescence spectra can be explained by the calculated electron spin-dependent optical transition probabilities based on the local-spin density approximation.     

Lipase TL-mediated kinetic tesolution of 5-benzyloxy-1-tert-butyldimethylsilyloxy-2-pentanol at low temperature: concise asymmetric synthesis of both enantiomers of a piperazic acid derivative

Lipase TL-mediated kinetic resolution of (+/-)-5-benzyloxy-1-tert-butyldimethylsilyloxy-2-pentanol (5) at low temperature proceeded to give the corresponding (S)-alcohol 5 and (R)-acetate 6 in quantitative yields with high enantiomeric purity. The addition of bases such as pyridine, DMAP, 2,4- and 2,6-lutidines, or triethylamine considerably enhanced the rate of kinetic resolution. The alcohol (S)-5 and the acetate (R)-6 were converted to piperazic acid derivatives (R)- and (S)-3, respectively, via the intramolecular Mitsunobu reaction as a key step.     

Ion-exchange resin decomposition in supercritical water

Abstract

Using supercritical water oxidation, the cation exchange resin was decomposed fast and completely to water, carbon dioxide and sulfuric acid. While the resin decomposition yield increased with the reaction time and the amount of hydrogen peroxide added as oxidizing agent, it was constant in the resin concentration from 0.14 to 1.9 dry resin weight percent to water. More than 99% of the cation exchange resin was decomposed with hydrogen peroxide added in the amount of 7 times the stoichiometric value at 673 K and 30MPa for 30 minutes of the reaction time. The cation exchange resin is decomposed through two main reaction pathways. One has a rate controlling intermediate such as acetic acid whose decomposition rate was very slow, and the other does not have stable intermediates. The decomposition of the acetic acid is a significant factor for the complete decomposition of the resin, although it does not dominate the whole resin decomposition. A simple kinetic model that estimates the resin decomposition yield was developed.     

Mechanistic study on dimerization of acetylene with a Nieuwland catalyst

A mechanistic study on the Nieuwland catalysis for dimerization of acetylene is performed by detecting copper–acetylene and copper–monovinylacetylene π‐complexes and also by examining the kinetics under virtually the same reaction conditions employed in the industrial process. An efficient H/D exchange occurs between acetylene and protons in the Nieuwland catalytic system. Addition of a coordinating ligand to the conventional Nieuwland catalytic system results in improvement of the catalytic activity and selectivity for the acetylene dimerization. The kinetic analysis including the kinetic deuterium isotope effect provides valuable insight into the Nieuwland catalytic mechanism of the dimerization of acetylene. Copyright © 2008 John Wiley & Sons, Ltd.