Preparation and chromatographic evaluation of a cysteine-bonded zwitterionic hydrophilic interaction liquid chromatography stationary phase.
ABSTRACT A cysteine-bonded zwitterionic hydrophilic interaction chromatography (HILIC) stationary phase (Click TE-Cys) was prepared based on the "thiol-ene" click chemistry. The Click TE-Cys material was characterized by solid state ¹³C cross polarization/magic-angle spinning (CP/MAS) NMR and elemental analysis. The dynamic evaluation for cytosine, cytidine and orotic acid was performed using Van Deemter plots. The plate height values were no more than 24 μm for the flow rate between 0.5 and 5.4 mm s⁻¹ (0.3-3.5 mL min⁻¹), which proved the excellent separation efficiency of Click TE-Cys stationary phase. The influences of the content of water, concentration of salt and pH of the buffer solution on the retention of model compounds were investigated. The results demonstrated that the separation of polar analytes was dominated by the partitioning mechanism, while the contribution of electrostatic interaction was minor. The thermodynamic characteristic of Click TE-Cys stationary phase was also studied according to van't Hoff plot. An exothermic process for transferring analytes from the mobile phase to the stationary phase was observed and a linear relationship for ln k and 1/T was achieved, indicating no change of retention mechanism within the measured temperature range. Besides, the zwitterionic stationary phase exhibited good stability. Considering the high hydrophilicity of Click TE-Cys stationary phase, the application in the separation of protein tryptic digests was carried out using hydrophilic interaction chromatography-electrospray ionization mass spectrometry (HILIC-ESI-MS). More peaks were adequately resolved on the Click TE-Cys column comparing with that on the TSK Amide-80 column. In addition, the orthogonality between HILIC and RPLC system was investigated utilizing geometric approach. The XTerra MS C₁₈ and Click TE-Cys column displayed great difference in separation selectivity, with the orthogonality reaching 88.0%. On the other hand, the orthogonality between Click TE-Cys and TSK Amide-80 system was 21.4%, i.e. the selectivity was similar but slightly different from each other. The successful separation of protein digests indicated the great potential of Click TE-Cys stationary phase in the separation of complex samples and applicability in two-dimensional liquid chromatography (2D-LC).
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Conference Proceeding: Counting distance permutations[show abstract] [hide abstract]
ABSTRACT: A distance permutation index supports fast proximity searching in a high-dimensional metric space. Given some fixed reference sites, for each point in a database the index stores a permutation naming the closest site, the second-closest, and so on. We examine how many distinct permutations can occur as a function of the number of sites and the size of the space. We give theoretical results for tree metrics and vector spaces with L<sub>1</sub>, L<sub>2</sub>, and L<sub>infin</sub> metrics, improving on the previous best known storage space in the vector case. We also give experimental results and commentary on the number of distance permutations that actually occur in a variety of vector, string, and document spaces.Data Engineering Workshop, 2008. ICDEW 2008. IEEE 24th International Conference on; 05/2008
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ABSTRACT: We introduce a new probabilistic proximity search algorithm for range and K-nearest neighbor (K-NN) searching in both coordinate and metric spaces. Although there exist solutions for these problems, they boil down to a linear scan when the space is intrinsically high-dimensional, as is the case in many pattern recognition tasks. This, for example, renders the K-NN approach to classification rather slow in large databases. Our novel idea is to predict closeness between elements according to how they order their distances towards a distinguished set of anchor objects. Each element in the space sorts the anchor objects from closest to farthest to it, and the similarity between orders turns out to be an excellent predictor of the closeness between the corresponding elements. We present extensive experiments comparing our method against state-of-the-art exact and approximate techniques, both in synthetic and real, metric and non-metric databases, measuring both CPU time and distance computations. The experiments demonstrate that our technique almost always improves upon the performance of alternative techniques, in some cases by a wide margin.IEEE Transactions on Pattern Analysis and Machine Intelligence 10/2008; 30(9):1647-58. · 4.80 Impact Factor
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ABSTRACT: We review the major paradigms for approximate similarity queries and propose a classification schema that easily allows existing approaches to be compared along several independent coordinates. Then, we discuss the impact that scheduling of index nodes can have on performance and show that, unlike exact similarity queries, no provable optimal scheduling strategy exists for approximate queries. On the positive side, we show that optimal-on-the-average schedules are well-defined and that their performance is indeed the best among practical schedules.Journal of Discrete Algorithms. 01/2009;