Steam distillation-solid-phase microextraction for the detection of Ephedra sinica in herbal preparations

A new method involving concurrent solid-phase microextraction combined with continuous hydrodistillation of essential oil was developed. This new methodology allowed for the detection by GC-MS of very small amounts of a diagnostic peak for the authentication of Ephedra sinica, in a short period of time and using only small sample sizes. This diagnostic peak was identified as 4-vinylanisole, and elucidated from the chromatographic profile allowed for the identification of a sample as E. sinica among other species investigated in this study. To the best of our knowledge this is the first report on using continuous solid-phase microextraction coupled to hydrodistillation for the investigation of essential oil components, and the first report of 4-vinylanisole as a marker compound for E. sinica. A total of 46 collections representing 21 species of Ephedra were studied.     

A chemometric study of active parameters and their interaction effects in a nebulized sheath-liquid electrospray interface for capillary electrophoresis-mass spectrometry

A chemometrics approach has been used for evaluating the effect of four experimental parameters when coupling capillary electrophoresis (CE) to electrospray ionization-mass spectrometry (ESI-MS). Electrospray voltage, sheath-liquid flow rate, nebulizing gas flow rate, and spray needle position in respect to the MS orifice were varied according to a full factorial design. In addition to main effects, two interaction effects could be identified as significant when measuring the peak intensity of the analytes, from a sample mixture containing peptides and pharmaceuticals. The first interaction effects, between the nebulizing gas flow rate and the sheath-liquid flow rate, and the second interaction effect, between the nebulizing gas flow rate and the spray position, could further explain the impact that these variables have on the spray performance. The number of theoretical plates and the baseline noise were also measured. The sheath-liquid flow was found to significantly affect the separation efficiency, while the noise level mainly was controlled by the nebulizing gas flow. The same factorial design was also used for a CE capillary with lower internal diameter (ID) and the effects of the same variables were compared on those capillaries using equal injection volume for both capillaries. Similar trends were obtained in both capillaries but capillary ID was shown to be a significant variable when evaluating both capillaries in a single model. It was found that a capillary with 25 microm ID provided improved CE-MS performance over than corresponding 50 microm ID capillary. Enhanced sensitivity was obtained using the narrow-bore capillary, and at lower sheath-liquid flow rate the 25 microm ID capillary also gave rise to more efficient peaks.     

Hierarchical porphyrin self-assembly in aqueous solution

In aqueous solution meso-tetrakis(4-phosphonatophenyl)porphyrin shows self-aggregation processes controlled by the "sergeant-soldier rule". After partial protonation of the external phosphonic groups, it is possible (i) to further protonate the inner nitrogen atoms of the molecules or (ii) to allow, over time, the system to aggregate. Therefore, the two procedure lead to a different system evolution, producing species with different chemico-physical properties.     

Two-dimensional protein map of human vastus lateralis muscle

Protein samples of human vastus lateralis muscle were analyzed by two-dimensional gel electrophoresis, using immobilized pH gradients encompassing several pH regions in the first dimension and sodium dodecyl sulfate-polyacrylamide gel electrophoresis in the second dimension. More than 500 protein spots on each gel were detected by silver staining, of which 150 were excised, digested in-gel with trypsin and characterized by matrix assisted laser desorptioin/ionization-mass spectrometry and tandem electrospray mass spectrometry. Using these techniques, 124 spots including contractile proteins and metabolic enzymes were identified. This database should provide a valuable resource for the definition of the functional properties of muscle fibres and for assessment of the influence of e.g., hypoxia, ischaemia and ageing on protein level.     

Direct detection of ion pairs by fluorescence enhancement

Sensor 1 signals the simultaneous presence of sodium and phosphate with an increased fluorescence signal in the manner of a photoionic AND logic gate.     

Infinitely many solutions of a symmetric semilinear elliptic equation on an unbounded domain

We study a semilinear elliptic equation of the form

Kazhdan-Lusztig Polynomials for 321-Hexagon-Avoiding Permutations

In (Deodhar, Geom. Dedicata, 36(1) (1990), 95–119), Deodhar proposes a combinatorial framework for determining the Kazhdan-Lusztig polynomials P _x , _w in the case where W is any Coxeter group. We explicitly describe the combinatorics in the case where (the symmetric group on n letters) and the permutation w is 321-hexagon-avoiding. Our formula can be expressed in terms of a simple statistic on all subexpressions of any fixed reduced expression for w. As a consequence of our results on Kazhdan-Lusztig polynomials, we show that the Poincaré polynomial of the intersection cohomology of the Schubert variety corresponding to w is (1+q) ^l(w) if and only if w is 321-hexagon-avoiding. We also give a sufficient condition for the Schubert variety X _w to have a small resolution. We conclude with a simple method for completely determining the singular locus of X _w when w is 321-hexagon-avoiding. The results extend easily to those Weyl groups whose Coxeter graphs have no branch points (B C _n , F ₄, G ₂).