Syntheses and cation binding properties of 12-membered ring nitrogen-pivot lariat ethers

The efficient synthesis of several 12-membered ring, N-pivot lariat ethers are reported and it is shown that binding to sodium cations is generally weak except when an oligoethyleneoxy sidearm is long enough to provide additional solvation.     

Amino acid analysis by derivatization with chromogenic 4-phenylazobenzyloxycarbonyl chloride (PAZ-Cl): Comparison of reversed-phases

Summary The chromogenic reagent 4-phenylazobenzyloxycarbonyl chloride (PAZ-Cl) was used for the automated pre-column derivatization of amino acids (AAs) at ambient temperature followed by liquid chromatographic separation of the derivatives formed.Since in previous investigations it was realised that the selectivity of a C-18 stationary phase decreased after 40 injections of PAZ-AAs the suitability of 12 reversedphases distinguished by silica modification, carbon content, and particle characteristics was tested. Among these columns only a polymer-coated C-18 stationary phase furnished satisfactory repeatability of retention times for 250 analyses.     

Synthesis and characterization of cross-linked reverse micelles

The design and synthesis of a new cross-linkable amphiphile is reported. Solutions of the amphiphile in a toluene/water mixture form reverse micelles as indicated by dynamic light scattering and NMR spectroscopy. As indicated by dynamic light scattering, TEM, and NMR spectroscopy data, these reverse micelles can be cross-linked without drastically changing the radius of the reverse micelles. Mixed reverse micelles are also characterized and cross-linked. The cross-linked reverse micelles are demonstrated to facilitate phase transfer and can be used to site isolate a catalyst.     

Detection of homocysteine and cysteine

At elevated levels, homocysteine (Hcy, 1) is a risk factor for cardiovascular diseases, Alzheimer's disease, neural tube defects, and osteoporosis. Both 1 and cysteine (Cys, 3) are linked to neurotoxicity. The biochemical mechanisms by which 1 and 3 are involved in disease states are relatively unclear. Herein, we describe simple methods for detecting either Hcy or Cys in the visible spectral region with the highest selectivity reported to date without using biochemical techniques or preparative separations. Simple methods and readily available reagents allow for the detection of Cys and Hcy in the range of their physiologically relevant levels. New HPLC postcolumn detection methods for biological thiols are reported. The potential biomedical relevance of the chemical mechanisms involved in the detection of 1 is described.     

One-pot multi-step synthesis: a challenge spawning innovation

Creating one-pot synthetic routes is a challenge that is already spawning new chemistry, enzymes, materials, and mechanistic insight. Through one-pot reactions, the chemical products that add value to our lives can be produced with less waste and greater economic benefits. Within this Emerging Area, we describe models for designing one-pot reactions as well as advanced catalysts created to facilitate their realization.     

Alternative approaches to infrared multiphoton dissociation in an external ion reservoir

In this work we present variations on in-hexapole infrared multiphoton dissociation (IRMPD) for the characterization of modified oligonucleotides using an ESI-FTICR spectrometer. We demonstrate that IRMPD in the external ion reservoir provides a comprehensive series of fragments allowing thorough characterization of a wide range of oligonucleotides containing alternative backbones and 2′ substitutions. An alternative pulse sequence is presented that allows alternating MS and IRMPD MS/MS spectra to be acquired on a chromatographic timescale without loss in ionization duty cycle. Ions are excited to a larger cyclotron radius such that they “dodge” the IR laser beam that travels through the center of the trapped ion cell and impinges on the external ion reservoir creating IRMPD fragments that will be detected in the next scan. An alternative approach for directing IR radiation into the external ion reservoir using a hollow fiber waveguide as a photon conduit is presented. This approach offers a simple and robust alternative to the previously utilized on-axis scheme and may allow effective implementation with lower power lasers owing to the inherent increase in power density achieved by focusing the nascent laser beam into the hollow fiber waveguide.