The Parametrically Forced Pendulum: A Case Study in 1 1/2 Degree of Freedom

This paper is concerned with the global coherent (i.e., non-chaotic) dynamics of the parametrically forced pendulum. The system is studied in a === degree of freedom Hamiltonian setting with two parameters, where a spatio-temporal symmetry is taken into account. Our explorations are restricted to large regions of coherent dynamics in phase space and parameter plane. At any given parameter point we restrict to a bounded subset of phase space, using KAM theory to exclude an infinitely large region with rather trivial dynamics. In the absence of forcing the system is integrable. Analytical and numerical methods are used to study the dynamics in a parameter region away from integrability, where the analytic results of a perturbation analysis of the nearly integrable case are used as a starting point. We organize the dynamics by dividing the parameter plane in fundamental domains, guided by the linearized system at the upper and lower equilibria. Away from integrability some features of the nearly integrable coherent dynamics persist, while new bifurcations arise. On the other hand, the chaotic region increases.2000 Mathematical Subject Classification: 37J20, 37J40, 37M20, 70H08.Dedicated to Professor Shui-Nee Chow on the occasion of his 60th birthday.     

Facile preparation of recyclable biocatalyst-decorated magnetic nanobeads in aqueous media

A facile process was developed to manufacture biocatalyst-conjugated magnetic nanobeads, which afford no loss of the intrinsic activity and enantioselectivity of biocatalysts. Up to 90% of their activities remained after six-time recycling in aqueous media.     

Analysis of chiral amino acids in cerebrospinal fluid samples linked to different stages of Alzheimer disease

Chiral micellar electrokinetic chromatography with laser-induced fluorescence detection (chiral-MEKC-LIF) was used to investigate D- and L-amino acid contents in cerebrospinal fluid (CSF) samples related to different Alzheimer disease (AD) stages. CSF samples were taken from (i) control subjects (S1 pool), (ii) subjects showing a mild cognitive impairment who remained stable (S2 pool), (iii) subjects showing an mild cognitive impairment that progressed to AD (S3 pool) and (iv) subjects diagnosed with AD (S4 pool). The optimized procedure only needed 10 μL of CSF and it included sample cleaning, derivatization with FITC and chiral-MEKC-LIF separation. Eighteen standard amino acids were baseline separated with efficiencies up to 703,000 plates/m, high sensitivity (LODs in the nM range) and good resolution (values ranging from 2.6 to 9.5). Using this method, L-Arg, L-Leu, L-Gln, γ-aminobutyric acid, L-Ser, D-Ser, L-Ala, Gly, L-Lys, L-Glu and L-Asp were detected in all the CSF samples. S3 and S4 samples (i.e. AD subjects) showed significant lower amounts of L-Arg L-Lys, L-Glu and L-Asp compared to the non-AD S1 and S2 samples, showing in the S4 group the lowest amounts of L-Arg L-Lys, L-Glu and L-Asp. Moreover, γ-aminobutyric acid was significantly higher in AD subjects with the highest amount also found for S4. No significant differences were observed for the rest of amino acids including D-Ser. Based on the obtained chiral-MEKC-LIF data, it was possible to correctly classify all the samples into the four groups. These results demonstrate that the use of enantioselective procedures as the one developed in this work can provide some new light on the investigations of AD, including the discovery of new biomarkers related to different stages of AD.     

High-performance liquid chromatography-diode array detection-electrospray ionization multi-stage mass spectrometric screening of an insect/plant system: the case of Spodoptera littoralis/Lycopersicon esculentum phenolics and alkaloids

High-performance liquid chromatography-diode array detection-electrospray ionization multi-stage mass spectrometry (HPLC-DAD-ESI-MS(n)) is considered to be a very valuable tool for the characterization of compounds found in trace amounts in natural matrices, as their previous isolation and clean-up steps can be avoided. Micro-scale separation increases the potential of this analytical technique, allowing the determination of compounds in reduced samples. Spodoptera littoralis represents a major challenge to Solanaceae plants, as it is one of the most deleterious pests. The S. littoralis/Lycopersicon esculentum system was studied for the first time concerning glycoalkaloids and phenolics. Using HPLC-DAD-ESI-MS(n) we were able to characterize 15 phenolic compounds in L. esculentum leaves. Nine of them are reported for the first time. Some differences were found between leaves of cerasiforme and 'Bull's heart' varieties. However, in the materials of S. littoralis (larvae, adults, exuviae and excrements) reared in both L. esculentum leaves no phenolics were identified. α-Tomatine was the main glycoalkaloid in the host plant. The glycoalkaloid composition of the different S. littoralis materials was distinct, with α-tomatine and dehydrotomatine being the main detected compounds in larvae and excrements. These results add knowledge to the ecological interaction in this insect/plant duo, for which it is hard to obtain considerable sample amounts.     

Use of triacylglycerol profiles established by high performance liquid chromatography with ultraviolet-visible detection to predict the botanical origin of vegetable oils

A method for the determination of triacylglycerols (TAGs) in vegetable oils from different botanical origins by HPLC with UV-vis detection has been developed. Using a core-shell particle packed column (C18, 2.6 μm), TAG separation was optimized in terms of mobile phase composition and column temperature. Using isocratic elution with acetonitrile/n-pentanol at 10 °C, excellent efficiency with good resolution between most of the TAG peak pairs, within a total analysis time of 15 min, was achieved. Using mass spectrometry detection, a total of 15 peaks, which were common to oils of six different botanical origins (corn, extra virgin olive, grapeseed, hazelnut, peanut and soybean) were identified. These peaks were used to construct linear discriminant analysis (LDA) models for botanical origin prediction. Ratios of the peak areas selected by pairs were used as predictors. All the oils were correctly classified with assignment probabilities higher than 95%.     

Sulfonamide carbazole receptors for anion recognition

Carbazole-based receptors functionalized with two sulfonamide groups have been synthesized and their properties as anion receptors have been evaluated. The receptor with bis(trifluoromethyl)aniline groups has shown a very high affinity for halide ions, especially remarkable as only two hydrogen bonds are formed in the complexes. (1)H NMR and fluorescence titrations have been carried out and binding constants up to 7.9 × 10(6) M(-1) have been reached. X-ray structures have been obtained and a modelling study has shown the possible reasons for the large affinity of these compounds for halide anions.     

Determination of organophosphorous pesticides in the ppq range using a simple solid-phase extraction method combined with dispersive liquid-liquid microextraction

Solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME) was applied for the extraction of six organophosphorous pesticides (OPPs) in water samples. The analytes considered in this study were determined by gas chromatography with mass spectrometry and included prophos, diazinon, chlorpyrifos methyl, methyl parathion, fenchlorphos and chlorpyrifos. Several extraction conditions (extraction solvent and elution/dispersion solvents nature, extraction solvent volume, elution solvent volume, water volume and sample volume) were tested for SPE-DLLME with these analytes and the best results were obtained using carbon tetrachloride as the extraction solvent and acetone as the elution/dispersion solvent. Calibration curves for the determination of OPPs in water samples were constructed in the concentration range of 10-100 ng/L. Limits of detection (LODs) ranged from 38 to 230 pg/L values that are below the maximum admissible level for drinking water (100 ng/L). Relative standard deviations (RSD) were between 8.6 and 10.4% for a fortification level of 100 ng/L. At the same fortification level, the relative recoveries (R.R.) of tap, well and irrigation water samples were in the range of 30.2-97.1%.     

Laser induced fluorescence spectroscopy of tetracene with large Ar, Ne, and H2 clusters in superfluid He nanodroplets

Clusters of tetracene molecules with different numbers of attached (Ar)(N), (Ne)(N) and (H(2))(N) particles (N = 1-2000) are assembled inside superfluid He nanodroplets and studied via laser-induced fluorescence. The frequency shift of the fluorescence spectrum of the tetracene molecules is studied as a function of cluster size and pickup order of tetracene and cluster species. For (Ar)(N) and (Ne)(N) clusters, our results indicate that the tetracene molecules reside inside the clusters when tetracene is captured by the He nanodroplet before the cluster species; conversely, the tetracene molecules stay on the surface of the clusters when tetracene is captured after the cluster species. In the case of (H(2))(N) clusters, however, tetracene molecules reside inside the (H(2))(N) clusters irrespective of the pickup order. We conclude that (Ar)(N) and (Ne)(N) clusters are rigid at T = 0.38 K, while (H(2))(N) clusters of up to N = 2000 remain fluxional at the same temperature. The results may also indicate the occurrence of heterogeneous nucleation of the (H(2))(N) clusters, which is induced by the interaction with tetracene chromophore molecules.     

Crystallization and characterization of an inflammatory lectin purified from the seeds of Dioclea wilsonii

DwL, a lectin extracted from the seeds of Dioclea wilsonii, is a metalloprotein with strong agglutinating activity against rabbit and ABO erythrocytes, inhibited by glucose and mannose. DwL was purified by affinity chromatography on a Sephadex G-50 column and ion exchange chromatography on a HiTrap SP XL column. SDS-PAGE revealed three electrophoretic bands corresponding to the α (25,634 ± 2 Da), β (12,873 ± 2 Da) and γ (12,779 ± 2 Da) chains. Protein sequencing was done by Tandem Mass Spectrometry. The primary sequence featured 237 amino acids and was highly homologous to other reported Diocleinae lectins. A complete X-ray dataset was collected at 2.0 ? for X-Man-complexed DWL crystals produced by the vapor diffusion method. The crystals were orthorhombic and belonged to the space group I222, with the unit-cell parameters a = 59.6, b = 67.9 and c = 109.0 ?. DWL differed in potency from other ConA-like lectins and was found to induce neutrophil migration in rats, making it particularly useful in structural/functional studies of this class of proteins.