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PubMed1995

Gel phase preference of ganglioside GM1 at low concentration in two-component, two-phase phosphatidylcholine bilayers depends upon the ceramide moiety.

In two-component phosphatidylcholine bilayers with coexisting liquid and P beta' gel phases, the distribution between phases of low concentrations of glycosphingolipids can be determined by freeze-etch electron microscopy after labeling the glycolipid with a suitable protein. We have found that the distribution depends upon the glycosphingolipid species (Rock, P. et al., (1991) Biochemistry 30, 19-25). Using this technique with cholera toxin as the protein label and bilayers formed from dipalmitoyl- and dielaidoylphosphatidylcholine (1:1) containing < 1 mol% GM1, we have studied the distribution of a family of GM1 homologues differing in the acyl chain and sphingoid base moieties. The GM1 preference for the P beta' ripple phase decreases with decreasing acyl chain length and increasing unsaturation. GM1 with either a C18:1 or C20:1 sphingoid base shows similar distributions in liquid and gel phases. When the molecules are preferentially found in the P beta' phase, they are positioned along unique loci in both A and A/2 forms of the ripple structure. This localization and acyl chain dependence reflect the volume, shape and localization of molecular packing defects in the P beta' phase. The ganglioside inclusions stabilize the P beta' phase and form compositional domains of unique topography.

Animals↗
PubMed1991

Effect of substitution of hydrogen oxide by deuterium oxide on thermotropic transition between the interdigitated gel phase and the ripple phase of dihexadecylphosphatidylcholine.

Thermotropic transitions of dihexadecylphosphatidylcholine (DHPC) dispersions in hydrogen oxide (1H2O) and deuterium oxide (2H2O) were investigated by differential scanning calorimetry (DSC). In DHPC dispersions, transition temperature between interdigitated gel phase (L beta I) and ripple phase (P beta') is lower in 2H2O than in 1H2O, and transition between the ripple phase (P beta') and fluid phase (L alpha) in 2H2O occurs at a temperature slightly higher than in 1H2O. In dipalmitoylphosphatidylcholine (DPPC) dispersions, on the other hand, transition temperature between lamellar gel phase (L beta') and ripple phase is higher in 2H2O than in 1H2O. These results suggest that the interdigitated gel phase is more stable in 1H2O than in 2H2O. To account for the shift of transition temperature by the water substitution, difference of interfacial energies between these aqueous environments is discussed.

Calorimetry, Differential Scanning↗
PubMed1986

Mechanical characteristics of phase II and phase III of the interdigestive migrating motor complex in dogs.

In conscious dogs certain parameters of the jejunal interdigestive phase II and phase III activity were studied by means of closely spaced strain gauges and videofluoroscopy. During phase III the frequency, force, and rise time of contractions and the contraction spread were increased, whereas the intercontractile intervals and the propagation velocity of contractions were diminished in comparison to phase II. The contraction waves of phase III were variable with regard to their length of spread and their rate of caudad migration. These two parameters adjusted the duration, the propagation velocity, and the length of the activity front. Propagation of contractions was sometimes interrupted by periods of uncoupling. Propagation velocities within contraction waves varied according to the pattern slow-fast-slow-fast, producing the videofluoroscopically observed roller coaster movements of the luminal contents. It is concluded that phase II and phase III are characterized not only by the occurrence of irregular and regular activity but by a significant change of a number of contraction parameters.

Animals↗
PubMed2003

Retention of 3,5-dinitrobenzoyl derivatives of linear alcohol polyethoxylates in reversed-phase liquid chromatographic system with acetonitrile-water mobile phase.

The influence of mobile phase composition (acetonitrile-water ratio) on the separation of derivatised linear alkyl polyethoxylates (LAEs) is evaluated using thermodynamic quantities (Gibbs energy, enthalpy and entropy). In comparison to homologue series of alcohols oligomers of LAEs show irregular chromatographic behaviour that is demonstrated in irregular changes of thermodynamic quantities. It might be explained considering an influence of some of the following processes or their combinations on the retention of LAEs. These processes are solvation of oxyethylene chains in mobile phase, their interaction with silanols on silica surface of stationary phase and possibly their conformation changes. The composition of a mobile phase affects the mentioned processes and that is why the retention of LAEs is strongly (for the reversed-phase system unusually) sensitive to this composition in the studied range (volume fraction of acetonitrile phi = 0.90, 0.96 and 0.98). The experimental data also support the idea of the active role of stationary phase in the reversed-phase system.

Acetonitriles↗
PubMed2005

Influence of mobile phase composition and thermodynamics on the normal phase chromatography of echinocandins.

In the normal phase preparative HPLC of fermentation derived echinocandins, resolution of key impurities from the product of interest, pneumocandin B(o), is accomplished using a ternary ethyl acetate/methanol/water mobile phase with silica gel as the sorbent. In this work, previous characterization of the system is extended to define the impact and role of water content on the separation efficiency and retention of pneumocandin B(o). Experimental results indicate that column efficiency, measured using both the product of interest and small molecule tracers (compounds used for pulse tests), is good despite the use of an irregular silica and unusually high levels (greater than 6%) of water in the mobile phase. In contrast to column efficiency measurements using small molecules (MEK and toluene), measurements performed with the product itself indicate improved efficiency with increasing water content of the mobile phase. Building on these results, a scale-up/scale-down protocol was developed based on measurements of column efficiency using theoretical plate counts determined with pneumocandin B(o). Since the solubility of pneumocandin B(o) in the ternary mobile phase is relatively low, a higher strength solvent with higher levels of methanol and water is employed for dissolution of the crude product at concentrations of up to 40g/L. The mismatch between the high strength solvent used for the feed introduction and the mobile phase has the potential to affect column performance. The impact of this mismatch using plate count measurements with the product at both analytical and semi-preparative scales was found not to be significant. Finally, a van't Hoff analysis was performed to characterize the thermodynamics of adsorption of pneumocandin B(o) on silica. The analysis shows that the adsorption process for pneumocandin B(o) on silica in the ternary solvent system is endothermic (DeltaH(ads)>0), implying that the adsorption is entropically driven. Results from an overall water balance across the column indicate significant enrichment of adsorbed water on the silica surface. These results further emphasize the importance of selective partitioning of water between the bulk mobile phase and the silica as a dominant factor in controlling retention.

Adsorption↗
PubMed2005

Chelates of cobalt(III) and iron(II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol as test probes for the characterization of chromatographic effects on a reversed-phase liquid chromatography stationary phase.

The chromatographic effects on a reversed-phase liquid chromatography (RPLC) phase were established with the use of chelates system: cobalt(III) and iron(II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol as the test probes. Both chelates have the same octahedral structure, M:L = 1:2, the former chelate is cationic and can be used to probe the ion-exchange phenomena on a RPLC phase, whereas the latter is not charged and can be used as reference molecule with respect to the charged one. Based on well-established LC phenomena referred in the literature, the suitability of the chelate system for examining some chromatographic effects was tested. It was concluded that the proposed test method is sensitive towards the ion-exchange phenomena on the LC phase and the hydrogen bonding between the solvent eluent and the LC phase. In addition, chromatographic effects due to the presence of ultrasonic field or due to the presence of aromatic amines in the eluent were observed with the help of the proposed test method. Based on molecular computation, the properties of chelates were compared with properties of quaternary amines, the probes most frequently used for testing LC phases, and the possible differences in an interaction of the mentioned compounds with a surface of a RPLC phase were indicated.

Azo Compounds↗
PubMed2004

A growth study of Coxiella burnetii Nine Mile Phase I and Phase II in fibroblasts.

Coxiella burnetii, a slow-growing, gram-negative, obligate intracellular bacterium, is the causative agent of Q fever in humans. The avirulent Phase II C. burnetii Nine Mile strain can invade and establish persistent infections in a wide variety of laboratory cell lines, and is generally considered to be easier to grow in culture than the wild-type Phase I organism. Efforts to improve Phase I organism yield in the BHK-21 cell line demonstrated that high CO2 conditions and the use of Dulbecco's modified Eagle's medium (DMEM) with 4.5 g/l glucose supplementation resulted in higher organism yields. Phase II organisms grown in the same cell line and conditions showed lower growth rates. Analysis revealed that increased average numbers of C. burnetii Phase I organisms within fibroblasts was due to higher growth rates within the hosts rather than to increased uptake or to increased cell-to-cell spreading. Addition of the nucleoside cytidine to the growth medium stimulated growth of Phase II but not Phase I organisms.

Animals↗
PubMed2004

Phase I and phase II metabolic activities are retained in liver slices from mouse, rat, dog, monkey and human after cryopreservation.

Precision-cut liver slices are described as a valuable tool for in vitro metabolism studies of potential drug candidates. Recently, some papers reported successful cryopreservation conditions for liver slices, facilitating a broader and more efficient use of the tissue (particularly of human origin). The aim of this study is to evaluate the effect of cryopreservation on both phase I and phase II metabolism in liver slices prepared from mouse, rat, dog, monkey and human, using rapid freezing in the presence of 18% DMSO. Glucuronidation and sulfation activities (phase II) in both freshly prepared and cryopreserved liver slices were determined by rapid LC-MS/MS analyses using 7-hydroxycoumarin as a marker substrate. Testosterone was used as a marker substrate for cytochrome P450 mediated drug metabolism (phase I). Although the metabolic patterns and rates varied among the different species, the phase I and phase II metabolic capacities of the liver slices were well maintained after cryopreservation. Despite the good biotransformation capacity of cryopreserved slices a decrease in viability, expressed as ATP content and LDH leakage, was observed. MTT reduction was well maintained after cryopreservation. The possibility to cryopreserve liver slices will allow a more efficient utilisation of tissue, in particular from human, but also from dog and monkey. Finally, cryopreserved liver slices from mouse, rat, dog, monkey and human with good phase I and II metabolism activities are a useful in vitro tool to compare metabolite profiles of new chemical entities between species.

Adenosine Triphosphate↗
PubMed2002

Chromatographic shape selectivity with carbon dioxide-acetonitrile mobile phases. Effect of mobile phase composition and density.

Trends in chromatographic shape selectivity with mobile phases consisting of mixtures of carbon dioxide and acetonitrile are investigated. Selectivity is evaluated as a function of mobile phase composition, temperature, and column bonding chemistry. SRM (standard reference material) 869a is used as a probe of shape selectivity, while the selectivity between triphenylene and o-terphenyl is used to investigate planarity selectivity. Four molecular mass 228 polyaromatic hydrocarbon isomers are used to investigate shape selectivity based on differences in length-to-breadth ratio. Shape selectivity trends as a function of temperature and column type are found to be similar to what is seen in reversed-phase liquid chromatography, while the trend seen as the amount of acetonitrile in the mobile phase increases is found to be different than in reversed-phase liquid chromatography. In addition, the effect of mobile phase density, i.e., solvent strength, on shape selectivity is investigated by examining shape selectivity as a function of density with neat carbon dioxide as the mobile phase.

Acetonitriles↗
PubMed1997

Stability of silica-based, endcapped columns with pH 7 and 11 mobile phases for reversed-phase high-performance liquid chromatography.

The goal of this study was to define practical conditions and limitations of using silica-based, endcapped bonded-phase columns in intermediate and higher pH environments for developing rugged HPLC methods. Bonded-phase degradation in this pH range is a result mainly of silica support dissolution; covalently-bound silane ligands are hydrolyzed very slowly if at all from silica supports at intermediate and higher pH. Based on rates of silica support dissolution determined by chemical measurements and comparable chromatographic studies, we now find that endcapping alkyl-bonded stationary phases increases column longevity at pH 7, compared to non-endcapped columns. As previously determined for non-endcapped packings, we also find that the type of silica support determines the stability of bonded-phase packings. Silicas made by the sol-gel process are more resistant to dissolution than supports made by a silicate-gel (xerogel) process. In addition, endcapping methods apparently affect column stability, with double-endcapping methods apparently superior to single-endcapping approaches. Degradation rates for several endcapped commercial bonded-phase C8 columns were found to be quite variable in highly aggressive pH 7 accelerated-lifetime tests. Column stability in the pH 7-11 range is enhanced by using buffers other than phosphate in the mobile phase, and by excluding higher column temperatures. Certain silica-based endcapped bonded-phase columns can be used for developing rugged methods to at least pH 11 when used with organic buffers at < or = 40 degrees C.

Buffers↗
PubMed1999

Molecular mechanism of retention in reversed-phase high-performance liquid chromatography and classification of modern stationary phases by using quantitative structure-retention relationships.

Quantitative structure-retention relationships (QSRRs) were derived for logarithms of retention factors normalised to a hypothetical zero percent organic modifier eluent, log kw, determined on 18 reversed-phase high-performance liquid chromatography (RP-HPLC) columns for 25 carefully designed, structurally diverse test analytes. The study was aimed at elucidating molecular mechanism of retention and at finding an objective manner of quantitative comparison of retention properties and classification of modern stationary phases for RP-HPLC. Three QSRR approaches were employed: (i) relating log kw to logarithms of octanol-water partition coefficient (log P); (ii) describing log kw in terms of linear solvation-energy relationship-based parameters of Abraham; (iii) regressing log kw against simple structural descriptors acquired by calculation chemistry. All the approaches produced statistically significant and physically interpretable QSRRs. By means of QSRRs the stationary phase materials were classified according to the prevailing intermolecular interactions in the separation process. Hydrophobic properties of the columns tested were parametrized. Abilities of individual phases to provide contributions to the overall retention due to non-polar London-type intermolecular interactions were quantified. Measures of hydrogen-bond donor activity and dipolarity of stationary phases are proposed along with two other phase polarity parameters. The parameters proposed quantitatively characterize the RP-HPLC stationary phases and provide a rational explanation for the differences in retention patterns of individual columns observed when applying the conventional empirical testing methods.

Chromatography, High Pressure Liquid↗
PubMed2001

Circadian phase shifting: Relationships between photic and nonphotic phase-response curves.

A variety of photic and nonphotic stimuli can phase-shift the mammalian circadian pacemaker. It has been suggested that the phase-response curves (PRCs) characterizing these diverse stimuli may comprise two major PRC families, one typified by the photic PRC describing the response to brief light pulses, and the other typified by the nonphotic PRC describing the response to stimuli evoking behavioral arousal and/or locomotor activity. Additionally, the mammalian circadian pacemaker can be phase-shifted by dark pulses presented on a constant-light (LL) background. While dark pulse-induced phase shifting was interpreted originally as a mirror-image photic effect, other observations suggest that the dark pulse PRC may instead belong to the family of nonphotic, activity-dependent PRCs. In a recent study, we reexamined the phase-shifting effects of dark pulses in the Syrian hamster, and concluded that the dark pulse PRC reflects both nonphotic and photic mirror-image mechanisms. In the current report, we reanalyze previously published hamster PRC data using polynomial curve-fitting procedures. The results of these analyses reveal that (a) the photic and nonphotic PRCs have identical shape but opposite phasing, and (b) the dark pulse PRC can be modeled by simple summation of nonphotic and photic mirror-image PRCs. This model predicts accurately the shape of the dark pulse PRC, particularly the extension of the phase-advance region into the subjective night.

Animals↗
PubMed2000

Kinetics of phase separation under different process and design parameters in aqueous two-phase systems.

A practical study is presented of the effect of height/diameter (H/D) ratio of settlers on the kinetics of phase separation in aqueous two-phase systems (ATPSs). Poly(ethylene glycol) (PEG) 1000-phosphate systems with the presence of undiluted and diluted whey and disrupted yeast were used in batch studies. The influence of the biological suspensions on the rate of phase separation was investigated. It was observed that, phase separation time is much faster when disrupted suspension was used. The addition of undiluted suspensions to ATPSs slowed the process of phase separation. When the batch settler with a large cross section area (H/D ratio less than one) was used, the phases separated much faster than in a settler with a H/D ratio greater than one. Conclusions are drawn concerning the characterisation of the process and design parameters involved in the phase separation for the design of appropriate equipment.

Kinetics↗
PubMed2000

Chiral separation by simultaneous use of vancomycin as stationary phase chiral selector and chiral mobile phase additive.

Improved chiral selectivity was observed for numerous compounds when vancomycin was added to the mobile phase on a Chirobiotic-V column. This chiral mobile phase additive (CMPA) is the same chiral selector as that bonded to the stationary phase of this Chirobiotic-V column. A substantial increase in the difference in enthalpy of transfer, deltadeltaH, and in the difference in entropy of transfer, deltadeltaS, for two enantiomers was observed when vancomycin was used as both the mobile phase and the stationary phase chiral selector. The importance of mobile phase composition, analytical column, CMPA concentration was investigated. Also, higher resolution was observed for the separations of acidic compounds when a fluidity enhancing solvent, such as fluoroform, was added into the mobile phase. However, the most commonly used fluidity enhancement solvent, CO2, was ineffective.

Adsorption↗
PubMedDate not supplied

Investigation of two phase flow and phase trapping by secondary imbibition within Fontainebleau sandstone.

Pulsed magnetic field gradient stimulated echo NMR is used to investigate the simultaneous flow of two phases (an aqueous phase and an hydrocarbon phase) within a strongly water-wet sample of Fontainebleau sandstone. The Fontainebleau sandstone is prepared in increasing steady-state water saturations by a secondary imbibition process. The increase in the water saturation causes an increasing fraction of the oil phase (non-wetting phase) to become trapped within the sample. The stimulated echo dependence on the gradient pulse area, q, is used to derive the displacement probability, PX, for a fixed observation time. These displacement probabilities clearly show the progressive trapping of the hydrocarbon phase with increasing steady-state water saturations. Quantitative measurements of the fraction of the oil phase trapped were made from the echo attenuation function Edelta(q), both as a function of water saturation and observation time.

Geologic Sediments↗
PubMed2001

Characterization of the polarity of reversed-phase liquid chromatographic stationary phases in the presence of 1-propanol using solvatochromism and multivariate curve resolution.

This work characterizes solvation effects in reversed-phase liquid chromatography in the presence of 1-propanol. The solvatochromic method combined with a multivariate curve resolution-alternating least-squares analysis method has been used to characterize two modified silica surfaces--phenyl bonded and C18 bonded silica in mobile-phase mixtures of methanol--water and acetonitrile--water in the presence of 1-propanol. The presence of a small amount of 1-propanol has been shown to affect mainly the polarity properties of the stationary phases while the mobile-phase properties are largely unaffected. The chain collapse mechanism for the C18 stationary phase at higher concentrations of water seems to be inhibited in the presence of 1-propanol, and partitioning is the predominant solute retention mechanism. The phenyl-based phase shows considerably different behavior from that of the C18 phase, and propanol appears to disrupt the pi-stacking interactions between the solute and the phenyl rings anchored to the silica support.

Journal Article↗
PubMed2001

Solid-state NMR characterization of amylose tris(3,5-dimethylphenylcarbamate) chiral stationary-phase structure as a function of mobile-phase composition.

Solid-state NMR (1H/13C CPMAS) was utilized to identify structural differences in amylose tris(3,5-dimethylphenylcarbamate) chiral stationary phase (Chiralpak AD), as a function of mobile-phase composition. Dry Chiralpak AD stationary phase displayed an amorphous CPMAS NMR spectrum. However, CPMAS spectra of Chiralpak AD flushed with organic mobile phases clearly displayed evidence of solvent complexes. Chiralpak AD flushed with nonpolar hexane exhibited solvent complexes with minimal structural perturbation. For Chiralpak AD flushed with hexane containing alcohol modifiers, however, solvent incorporation caused significant difference in conformation distribution as evidenced by increased resolution of 13C peaks in the CPMAS spectrum of the stationary phase. 2-Propanol modifier displayed more efficient displacement of incorporated hexane while forming relatively more distinct/ordered solvent complexes with Chiralpak AD in comparison to ethanol modifier. Reversed elution order and unusual retention behavior on Chiralpak AD as a function of mobile-phase modifier was reported earlier. These chromatographic behaviors are believed to be due to different alterations of the steric environment of the chiral cavities in the CSP by the different mobile-phase modifiers. In addition, on the basis of the chemical shift of C-1 carbon on the amylose backbone, it is possible that Chiralpak AD's structure is a helix with a number of fold less than six.

Journal Article↗
PubMed2002

Highly cross-linked self-assembled monolayer stationary phases: an approach to greatly enhancing the low pH stability of silica-based stationary phases.

A new type of silica-based stationary phase with dramatically improved acid stability compared to any currently available silica-based stationary phase has been developed. Superior low pH stability is achieved by first self-assembling a densely bonded monolayer of (chloromethyl)-phenylethyltrichlorosilane (CMPES). The self-assembly step is followed by a Friedel-Crafts cross-linking of the reactive moieties with their neighbors, by addition of secondary, cross-linkable aromatic reagents, or by both. This phase is not endcapped. Elemental analysis data shows that an aluminum chloride catalyst is very effective at bonding aromatic cross-linking reagents, such as styrene heptamer and triphenylmethane, to the reactive CMPES monolayer. The stability of the retention factor of decylbenzene on the cross-linked self-assembled CMPES phases is compared to a sterically protected C18 phase to illustrate its superior resistance to acid-catalyzed-phase loss. Inverse size exclusion chromatography and flow-curve comparisons of the cross-linked self-assembled CMPES and the sterically protected C18 stationary phases illustrate their similar chromatographic efficiency.

Journal Article↗