Direct Correlation of Surface Tension and Surface Composition of Ionic Liquid Mixtures—A Combined Vacuum Pendant Drop and Angle-Resolved X-ray Photoelectron Spectroscopy Study

We investigated the surface tension and surface composition of various mixtures of the two ionic liquids (ILs) 1-methyl-3-octyl-imidazolium hexafluorophosphate [C₈C₁Im][PF₆] and 1,3-bis(polyethylene glycol)imidazolium iodide [(mPEG₂)₂Im]I in the temperature range from 230 to 370 K under ultraclean vacuum conditions. The surface tension was measured using a newly developed apparatus, and the surface composition was determined by angle-resolved X-ray photoelectron spectroscopy (ARXPS). In the pure ILs, the alkyl chains of [C₈C₁Im][PF₆] and the PEG chains of [(mPEG₂)₂Im]I are enriched at the IL/vacuum interface. In the mixtures, a strong selective surface enrichment of the alkyl chains occurs, which is most pronounced at low [C₈C₁Im][PF₆] contents. For the surface tension, strong deviations from an ideal mixing behaviour take place. By applying a simple approach based on the surface composition of the mixtures as deduced from ARXPS, we are able to predict and reproduce the experimentally measured temperature-dependent surface tension values with astonishingly high accuracy.     

Triflamidation of Allyl-Containing Substances:Unusual Dehydrobromination vs. Intramolecular Heterocyclization

Allyl halides with triflamide under oxidative conditions form halogen-substituted amidines. Allyl cyanide reacts with triflamide in acetonitrile or THF solutions in the presence of NBS to give the products of bromotriflamidation with a solvent interception, whereas in CH₂Cl₂ two regioisomers of the bromotriflamidation product without a solvent interception were obtained. The formed products undergo base-induced dehydrobromination to give linear isomers with the new C=C bond conjugated either with the nitrile group or the amidine moiety or alkoxy group. Under the same conditions, the reaction of allyl alcohol with triflamide gives rise to amidine, which was prepared earlier by the reaction of diallyl formal with triflamide. Unlike their iodo-substituted analogs, bromo-substituted amidines successfully transform into imidazolidines under the action of potassium carbonate.     

Effects of Hydrogen Peroxide on In Vitro Cultures of Tea (Camellia sinensis L.) Grown in the Dark and in the Light: Morphology,Content of Malondialdehyde,and Accumulation of Various Polyphenols

Tea plants (Camellia sinensis L.) are phenol-accumulating crops that are widely used for public health. The healing effect of tea leaf products is due to the biosynthesis of such phenolic compounds (PCs) as flavans, which have P-vitamin capillary-strengthening activity. Due to their limited habitat and the value of their specialized metabolites of a phenolic nature, a promising approach is to establish in vitro cultures from them that retain the ability to form PCs, which is characteristic of ex vivo tea plants. The aim of this study was to investigate the effect of exogenic H₂O₂ (0.01 mM; 0.1 mM; 1 mM) on the growth, morphology, degree of stress response, and accumulation of various phenolic compounds in tea plant callus cultures of different ages (24 or 36 days) grown under different cultivation conditions (darkness or light). According to the results obtained, the H₂O₂ effect on tea callus cultures of different ages did not cause changes in their morphophysiological characteristics, both after 2 h of exposure (rapid response of callus culture, RRCC) and after 48 h (delayed response of callus culture, DRCC). The determination of the malondialdehyde (MDA) content, which serves as an indicator of changes in the level of lipid peroxidation (LPO) and the presence of stress responses in plant cells, indicated either its maintenance at the control level, a decrease, or an increase. All these effects depended on the growth conditions of the tea callus cultures (darkness or light), their age, the duration of exposure (rapid or delayed response), and the H₂O₂ concentration. Similar trends were noted for the total content of PCs as well as the amount of flavans, proanthocyanidins (soluble and insoluble forms), and lignin. The plant cell responses reflected changes in its adaptation programs, when specialized metabolites act as a target for the action of H₂O₂, thereby contributing to an increase in their resistance.     

Ganglioside analysis by thin-layer chromatography matrix-assisted laser desorption/ionization orthogonal time-of-flight mass spectrometry

Metastable decomposition of ions generated in matrix-assisted laser desorption/ionization (MALDI) mass spectrometers complicates analysis of biological samples that have labile bonds. Recently, several academic laboratories and manufacturers of commercial instruments have designed instruments that introduce a cooling gas into the ion source during the MALDI event and have shown that the resulting vibrational cooling stabilizes these labile bonds. In this study, we compared stabilization and detection of desorbed gangliosides on a commercial orthogonal time-of-flight (oTOF) instrument with results we reported previously that had been obtained on a home-built Fourier transform mass spectrometer. Decoupling of the desorption/ionization from the detection steps resulted in an opportunity for desorbing thin-layer chromatography (TLC)-separated gangliosides directly from a TLC plate without compromising mass spectral accuracy and resolution of the ganglioside analysis, thus coupling TLC and oTOF mass spectrometry. The application of a declustering potential allowed control of the matrix cluster and matrix adduct formation, and, thus, enhanced the detection of the gangliosides.     

Character formulas for some classes of atypical gl(m+nε)- and p(m)-modules

If p is an arbitrary parabolic subsuperalgebra of g = gl(m + n), p(m), a character formula for the generic finite-dimensional irreducible g-module, such that p is the stabilizer of its lowest weight space, is announced. Furthermore, an estimate for the character of any finite-dimensional irreducible g-module in terms of its highest weight with respect to a distinguished Borel subsuperalgebra is presented (inequality (4)) and a sufficient condition for this to be an equality is found. In this way, two generalizations of the Kac character formula for typical modules are obtained: a formula concerning an arbitrary Borel subsuperalgebra ((1)) and a more effective formula ((3)) for the special case of a distinguished Borel subsuperalgebra. The complete proofs will appear in [14].Partially supported by Contract 911/11.04.88 with the Bulgarian Ministry of Culture, Science, and Education.     

The International Atomic Energy Agency's program on analytical quality control

For more than thirty years the International Atomic Energy Agency has been assisting laboratories in Member States in maintaining and improving the reliability, i.e. the quality of analyses of nuclear, industrial, environmental and biological materials, and materials of marine origin. Through the Analytical Quality Control Services (AQCS) the Agency initiates and supports improvements in the accuracy of analytical chemical and radiometric measurements and their traceability to basic standards. This is achieved by organizing worldwide and regional intercomparison exercises and by distributing reference materials. The latest biological and environmental reference and intercomparison materials are presented and general information is given on the preparation of materials, intercomparison runs, and the evaluation of reference data. Means to improve the quality of intercomparison results are presented and discussed.     

Extreme Value Asymptotics for Multivariate Renewal Processes

For a sequence of partial sums ofd-dimensional independent identically distributed random vectors a corresponding multivariate renewal process is defined componentwise. Via strong invariance together with an extreme value limit theorem for Rayleigh processes, a number of weak asymptotic results are established for thed-dimensional renewal process. Similar theorems for the estimated version of this process are also derived. These results are suggested to serve as simultaneous asymptotic testing devices for detecting changes in the multivariate setting.     

Cyclisation reactions of bis-protected guanidines

The cyclisation of N-allyl- and N-homoallylguanidines using DMDO or I₂/K₂CO₂ leading to novel heterocycles is reported.     

Synthesis of poly(ester amide)s with lateral groups from a bulk polycondensation reaction with formation of sodium chloride salts

Poly(ester amide)s with a regular sequence and derived from diamine, dicarboxylic acid, and glycolic acid units can be easily synthesized by using a thermal polycondensation method based on the formation of metal halide salts as a driving force. These new poly(ester amide)s have tuneable properties depending on the number of methylene groups and constitute a group of materials with potential interest as biodegradable materials in applications such as surgical sutures. The present work reveals that the proposed synthesis can also be applied when esters of L ‐lysine are used as a diamine unit since no secondary reactions such as transesterification occur under the required polymerization conditions. The possibility of linking compounds with pharmacological activity to the carboxylic acid groups of lysine extends the interest of the referred materials, for example, as drug delivery systems. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 661–667, 2008     

Extraction of cellulose and preparation of nanocellulose from sisal fibers

In this work a study on the feasibility of extracting cellulose from sisal fiber, by means of two different procedures was carried out. These processes included usual chemical procedures such as acid hydrolysis, chlorination, alkaline extraction, and bleaching. The final products were characterized by means of Thermogravimetric Analysis (TGA), Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), Differential Scanning Calorimetry (DSC) and Scanning Electronic Microscopy (SEM). The extraction procedures that were used led to purified cellulose. Advantages and disadvantages of both procedures were also analyzed. Finally, nanocellulose was produced by the acid hydrolysis of obtained cellulose and characterized by Atomic Force Microscopy (AFM).