Performance of different separation methods interfaced in the same MS-reflection TOF detector: a comparison of performance between CE versus HPLC for biomarker analysis

One of the aims in the field of proteomics is the identification of a protein or polypeptide, or a range of these compounds, that could provide pre-symptomatic indication of the onset of a disease. A number of analytical techniques have been employed to try and achieve this end. These techniques have been applied to the complete range of body fluids and tissues that are readily available from clinical studies. Of these sample sources, the urinary low molecular weight peptidome has been shown to reflect changes in the health status of the individual. The alterations that occur in the polypeptide make up of urine, which reflect changes in biological status, are known as biomarkers. To be able to determine these changes no single technique has emerged that can cope with detecting the large number of peptides present and quantifying them over the wide concentration range they exist in. In this investigation, we made use of a single reflectron time of flight (RTOF)-MS analyser to which we first connected a CE system and then a nanoflow HPLC. Two pooled male and female standard urine samples were compared on these systems. Both techniques had similar results in terms of number of peptides detected and the mass range the peptides were detected over. The major differences in terms of biomarker research were the ability in CE to calibrate the migration time of the peptides to allow comparison between samples. In addition, CE was shown not to suffer from carry over from previous samples as was seen in the LC analysis.     

Dynamic Covalent Synthesis of Donor–Acceptor Interlocked Architectures in Solution and at the Solution:Surface Interface

Despite advances in the range of mechanically interlocked architectures that can be synthesized and operated as supramolecular machines, motors and sensors in solution, in many cases their synthesis is laborious and expensive requiring long multistep pathways with extensive purification at each stage. Dynamic covalent chemistry has been shown to overcome problems with traditional kinetically controlled synthetic approaches that often afford low yields of interlocked architectures due to irreversible formation of non‐interlocked by‐products. Herein, we describe the use of reversible disulfide exchange reactions as a means to assemble catenanes and rotaxanes in organic solutions. Moreover, the application of this thermodynamic approach to assemble interlocked architectures at the solution:surface interface, specifically polymer resins, is discussed.     

Frequency permutation arrays

Motivated by recent interest in permutation arrays, we introduce and investigate the more general concept of frequency permutation arrays (FPAs). An FPA of length n = mλ and distance d is a set T of multipermutations on a multiset of m symbols, each repeated with frequency λ, such that the Hamming distance between any distinct x,y ∈ T is at least d. Such arrays have potential applications in powerline communication. In this article, we establish basic properties of FPAs, and provide direct constructions for FPAs using a range of combinatorial objects, including polynomials over finite fields, combinatorial designs, and codes. We also provide recursive constructions, and give bounds for the maximum size of such arrays. © 2006 Wiley Periodicals, Inc. J Combin Designs 14: 463–478, 2006