Rapid differentiation of isobaric and positional isomers of structurally related glycosides from Phytolacca bogotensis

Through the action of glycosyltransferases, a plant can biosynthetically assemble small different aglycons or 'templates' to various polysaccharides to produce numerous glycoconjugates differing in the type of the attached aglycon, the anomeric configuration of C‐1 of the glycosylating sugar, the type of sugar and the different position of attachments of the sugar unit present in the polysaccharide chain. The position of attachments and the anomeric configuration of the different sugar present in the polysaccharide create the opportunity to generate molecules with either the same or very close molecular weights, which have relative structural similarity – forming isobaric and positional isomers. Although isomeric differentiation was once considered outside of the domain of mass spectrometry, this task can now be resolved using tandem mass spectrometry. In a standardized purified glycoconjugate fraction (SPT01) from Phytolacca bogotensis, we report conventional electrospray ionization mass spectrometry and collision‐induced dissociation (CID) MS/MS parameters which favored the formation of characteristic product ions. This allowed us to suggest the type of sugar linkages present in a specific glycoconjugate. Ten new glycoconjugate are described from this plant and another twelve known saponins were structurally characterized using the automatic MSⁿ acquisition mode. The differentiation of two pairs of positional isomers and four isobaric glycosides and the production of a library of 30 glycosides present in P. bogotensis were accomplished. Copyright © 2009 John Wiley & Sons, Ltd.     

Rietveld refinement and activity of CO oxidation over Pd/Ce0.8Zr0.2O2 catalyst prepared via a surfactant-assisted route

A surfactant-assisted preparation method was successfully used to synthesize the Ce_0.8Zr_0.2O₂ nanophases that had homogeneous chemical composition, enhanced thermal stability and improved catalytic activity. Structural refinement by the Rietveld method confirmed that many cationic lattice defects were formed in the ceria-zirconia crystals due to incorporation of the cationic surfactant in the network of the solid. Zirconium dissolving into cubic structure of ceria improved its thermal stability but led to structure distortion. FT-IR in situ characterization showed that CO chemisorption on the palladium loaded ceria-zirconia catalyst formed linear and multibonded CO–metal complexes. It was also evidenced that CO₂ was produced in the CO chemisorption procedure from the pathways of CO disproportionation and CO reacting with lattice oxygen of the catalyst. Owing to high dispersion of the loaded metal palladium and defective structure of the ceria-zirconia support, the Pd/Ce_0.8Zr_0.2O₂ catalyst calcined at a temperature range between 873 and 1173 K not only exhibited a more stable catalytic activity for CO oxidation but also performed a lower light-off temperature at cool start below 373 K in comparison with Pd/CeO₂.     

Cryptanalyzing an improved security modulated chaotic encryption scheme using ciphertext absolute value

This paper describes the security weakness of a recently proposed improved chaotic encryption method based on the modulation of a signal generated by a chaotic system with an appropriately chosen scalar signal. The aim of the improvement is to avoid the breaking of chaotic encryption schemes by means of the return map attack introduced by Pérez and Cerdeira. A method of attack based on taking the absolute value of the ciphertext is presented, that allows for the cancellation of the modulation scalar signal and the determination of some system parameters that play the role of system key. The proposed improved method is shown to be compromised without any knowledge of the chaotic system parameter values and even without knowing the transmitter structure.     

Nuclear, chemical, and physical characterization of nuclear materials

The goal of nuclear forensics is to establish an unambiguous link between illicitly trafficked nuclear material and its origin. The Los Alamos National Laboratory (LANL) Nuclear Materials Signatures Program has implemented a graded “conduct of operations” type analysis flow path approach for determining the key nuclear, chemical, and physical signatures needed to identify the manufacturing process, intended use, and origin of interdicted nuclear material. This analysis flow path includes both destructive and non-destructive characterization techniques and has been exercized against different nuclear materials from LANL’s special nuclear materials archive. Results obtained from the case study will be presented to highlight analytical techniques that offer the critical attribution information.     

Assessment of processing and polymorphic form effect on the powder and tableting properties of microcrystalline celluloses I and II

Microcrystalline cellulose I (MCCI) is an excipient used as a diluent, disintegrant, glidant and binder for the production of pharmaceutical tablets. In this work, microcrystalline cellulose II (MCCII) was obtained from cotton fibers by basic treatment with 7.5 N NaOH followed by an acid hydrolysis. MCCI and MCCII materials were processed by wet granulation, dry granulation and spray drying. Either the polymorphic form or processing had no effects on the particle morphology or particle size. However, MCCII powders had a higher porosity, less packing tendency, degree of crystallinity, degree of polymerization and density, but a faster disintegration than MCCI. The tensile strength of MCCI was highly affected by the wet and dry granulation processes. Most of the resulting powder and tableting properties were dependent on the polymorphic form of cellulose, rather than on the processing employed.     

Electrochemical anion sensing using electrodes chemically modified with Au(I)–Cu(I) heterotrimetallic alkynyl cluster complexes containing ferrocenyl groups

A novel family of electrochemical anion sensors operating in aqueous media, based on the heterometallic Au(I)–Cu(I) [{Au₃Cu₂(C₂R)₆}Au₃(PPh₂C₆H₄PPh₂)₃](PF₆)₂ (L1, R = Fc; L2, R = C₆H₄Fc) alkynyl cluster complexes, is presented. Upon attachment to graphite and gold electrodes, these compounds exhibit a well-defined, essentially reversible, solid-state electrochemistry in contact with aqueous media, based on ferrocenyl-centered oxidation processes involving anion insertion, leading to distinctive pH-independent electrochemical responses for fluoride, chloride, bromide, perchlorate, bicarbonate, carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate, and nitrate anions. Cluster-modified electrodes can be used as potentiometric sensors as a result of the reversible, diffusion-controlled electrochemistry obtained for the anion-assisted electrochemical oxidation of L1 and L2.     

Biotransformation of mycosporine like amino acids (MAAs) in the toxic dinoflagellate Alexandrium tamarense

Changes in mycosporine-like amino acids (MAAs) induced by the increase of photosynthetically active radiation (PAR) were studied in the toxic dinoflagellate Alexandrium tamarense. Cultures of A. tamarense were maintained at exponential growth under low (25 micromol quanta m(-2)s(-1)) PAR irradiance. The cultures were nutrient enriched and one day later exposed to higher irradiance (150 micromol quanta m(-2)s(-1)). The content of MAAs was determined by means of high performance liquid chromatography (HPLC). Eleven MAAs, including some partially characterized compounds, were identified. The MAAs synthesis induction can be described as a two-stage process. The first one involves the net synthesis of the MAAs bi-substituted by amino acids. In the second stage these compounds were transformed into other secondary MAAs. The two most prominent changes were observed in the concentration of porphyra-334 and palythene. The cellular concentration of porphyra-334 increased during the first 2h of exposure to higher irradiance and then decreased rapidly. In contrast, the cellular concentration of palythene showed a continuous accumulation since the beginning of the exposure. In A. tamarense the main route of MAAs transformation has porphyra-334 as a precursor of a sequential conversion resulting in the accumulation of palythene.     

Cichoń’s diagram for uncountable cardinals

We develop a version of Cichoń’s diagram for cardinal invariants on the generalized Cantor space 2 ^κ or the generalized Baire space κ ^κ , where κ is an uncountable regular cardinal. For strongly inaccessible κ, many of the ZFC-results about the order relationship of the cardinal invariants which hold for ω generalize; for example, we obtain a natural generalization of the Bartoszyński–Raisonnier–Stern Theorem. We also prove a number of independence results, both with < κ-support iterations and κ-support iterations and products, showing that we consistently have strict inequality between some of the cardinal invariants.     

A Parallel Multilevel Metaheuristic for Graph Partitioning

One significant problem of optimisation which occurs in many scientific areas is that of graph partitioning. Several heuristics, which pertain to high quality partitions, have been put forward. Multilevel schemes can in fact improve the quality of the solutions. However, the size of the graphs is very large in many applications, making it impossible to effectively explore the search space. In these cases, parallel processing becomes a very useful tool overcoming this problem. In this paper, we propose a new parallel algorithm which uses a hybrid heuristic within a multilevel scheme. It is able to obtain very high quality partitions and improvement on those obtained by other algorithms previously put forward.     

Determination of gold and silver in copper concentrates, using k0 based neutron activation analysis

Procedures for the determination of gold and silver in copper concentrates, using k ₀ based neutron activation analysis, were developed and tested. The effects of gamma-ray self attenuation, neutron self-shielding and spectral interference were considered; precision, accuracy, and detection limits were studied by repeated analysis of copper concentrate internal reference materials. The analytical results have shown good precision and satisfactory accuracy in concordance with the detection limit and range of concentration.