Separation of therapeutic peptides with cyclofructan and glycopeptide based columns in hydrophilic interaction liquid chromatography.

Three cyclofructan-based, two glycopeptide-based, and one zwitterionic column used in the HILIC mode were assessed within a graphical framework based on different functional characteristics contributing to selectivity. The characteristics of these six HILIC columns are put in the perspective of 33 columns evaluated previously. The isopropyl carbamate modified cyclofructan 6 (CF6) stationary phase, Larihc P, showed reduced component contributions for hydrophilicity and hydrogen bonding relative to the native cyclofructan 6 column (Frulic N). Both Frulic N and Larihc P exhibited cation exchange attributed primarily to deprotonation of residual unsubstituted silica with the greater exchange ascribed to the reduced loading of CF6 observed for Larihc P. The cyclofructan 6 column with a polymeric styrene divinylbenzene support (MCI GEL™ CRS100) showed distinct selectivities consistent with its decreased cation exchange attributable to its nonionic core. The Chirobiotic T, Chirobiotic V, and ZI-DPPS columns displayed hydrophilicity and ion exchange selectivities similar to other zwitterionic stationary phases. All of the more hydrophilic columns showed excellent separation for the four classes of therapeutic peptides investigated: microbial secondary metabolites used as immune suppressants, synthetic gonadotropin hormones, synthetic cyclic disulfide-linked hormone-regulating hormones, and non-ribosomally derived polycyclic antibiotics. Resolution provided by these columns and ZIC-HILIC is compared for each class of peptide. Frulic N is primarily suitable for use in the HILIC mode whereas Chirobiotic T, because of its increased efficiency and selectivity, can be useful in both HILIC and reverse phase modes. In some Chirobiotic T applications, addition of low levels of a strong additive (trifluoroacetic acid, formic acid, etc.) to the mobile phase can be beneficial. In these peptide analyses, a relative weakening of the often-dominant ionic interaction between analyte and residual charge on the stationary phase improved resolution and selectivity.

Diffusion of methane and carbon dioxide in carbon molecular sieve membranes by multinuclear pulsed field gradient NMR.

Carbon molecular sieve (CMS) membranes are promising materials for energy efficient separations of light gases. In this work, we report a detailed microscopic study of carbon dioxide and methane self-diffusion in three CMS membrane derived from 6FDA/BPDA(1:1)-DAM and Matrimid polymers. In addition to diffusion of one-component sorbates, diffusion of a carbon dioxide/methane mixture was investigated. Self-diffusion studies were performed by the multinuclear (i.e., (1)H and (13)C) pulsed field gradient (PFG) NMR technique which combines the advantages of high field (17.6 T) NMR and high magnetic field gradients (up to 30 T/m). Diffusion measurements were carried out at different temperatures and for a broad range of the root-mean-square displacements of gas molecules inside the membranes. The diffusion data obtained from PFG NMR are compared with the corresponding results of membrane permeation measurements reported previously for the same membrane types. The observed differences between the transport diffusivities and self-diffusion coefficients of carbon dioxide and methane are discussed.

Sorbate Transport in Carbon Molecular Sieve Membranes and FAU/EMT Intergrowth by Diffusion NMR.

In this paper we present and discuss selected results of our recent studies of sorbate self-diffusion in microporous materials. The main focus is given to transport properties of carbon molecular sieve (CMS) membranes as well as of the intergrowth of FAU-type and EMT-type zeolites. CMS membranes show promise for applications in separations of mixtures of small gas molecules, while FAU/EMT intergrowth can be used as an active and selective cracking catalyst. For both types of applications diffusion of guest molecules in the micropore networks of these materials is expected to play an important role. Diffusion studies were performed by a pulsed field gradient (PFG) NMR technique that combines advantages of high field (17.6 T) NMR and high magnetic field gradients (up to 30 T/m). This technique has been recently introduced at the University of Florida in collaboration with the National Magnet Lab. In addition to a more conventional proton PFG NMR, also carbon-13 PFG NMR was used.