Biomedical subjects

Lane C Sander

Publications and source records attributed to Lane C Sander.

At least 19 recordsLinked to original sources

PubMed2006

Improved liquid chromatography methods for the separation and quantification of biotin in NIST standard reference material 3280: multivitamin/multielement tablets.

Two independently developed liquid chromatography (LC) methods for the quantitative determination of biotin in multivitamin/multielement tablets (NIST Standard Reference Material 3280 (SRM 3280)) are described. The methods use distinctly different tablet extraction solvents (methanol vs 1.5% aqueous formic acid) and analyte detection principles (mass spectrometry (MS) versus evaporative light-scattering detection (ELSD)) to ensure quantitative reliability. The use of different extraction and detection procedures allows cross-validation of the methods and enhances confidence in the final quantitative results. Both methods yield highly comparable results for the mean level of biotin (LC/MS = 26.5 mg/kg +/- 0.3 mg/kg (n = 12); LC/ELSD = 24.7 mg/kg +/- 1.7 mg/kg (n = 12)) in SRM 3280, yet the methods differ considerably in their analytical characteristics. The isotope-dilution LC/MS method exhibits excellent linearity from 0.02 ng to 77 ng biotin on-column with a method limit of detection (LOD) and limit of quantification (LOQ) of 0.02 ng (S/N > 3) and 0.06 ng (S/N > 10) biotin on-column, respectively. The LC/ELSD method exhibits good linearity from 155 ng to 9900 ng biotin on-column with a method LOD and LOQ of 155 ng (S/N > 3) and 310 ng (S/N > 10) biotin on-column, respectively. Method performance data indicates that the LC/MS method is analytically superior to the LC/ELSD method; however, either method in combination with SRM 3280 should provide quality assurance, accuracy, and traceability for biotin levels in multivitamin/multielement dietary supplements.

Biotin↗

PubMed2006

Analysis of hexabromocyclododecane diastereomers and enantiomers by liquid chromatography/tandem mass spectrometry: chromatographic selectivity and ionization matrix effects.

Hexabromocyclododecane (HBCD) is a flame retardant that is undergoing environmental risk assessment. The liquid chromatographic retention and electrospray ionization matrix effects were investigated for HBCD methods of analysis for environmental matrices. Column selectivity towards HBCD diastereomers was evaluated for C30 and C18 stationary phases under different mobile phase conditions and column temperatures. The HBCD elution order was dependent on the shape selectivity of the stationary phase and the mobile phase composition. Greater resolution, on columns with reduced shape selectivity, of beta-HBCD and gamma-HBCD was achieved with the use of an acetonitrile/water (compared with a methanol/water) mobile phase composition. A liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) method for the analysis of HBCD in biological tissues was evaluated for potential matrix effects. The influence of extracted matrix components on HBCD diastereomer and enantiomer analysis was investigated using a postextraction addition approach. Although the analysis of HBCD diastereomers was relatively unaffected by the sample matrix, the responses of the HBCD enantiomers in tissue samples were significantly influenced by matrix effects and other changes to the ionization conditions. The use of racemic 13C-labeled HBCD diastereomers as internal standards for enantiomer fraction measurements corrected for the changes in the mass spectrometer response.

Acetonitriles↗

PubMed2006

Quantitative determination of folic acid in multivitamin/multielement tablets using liquid chromatography/tandem mass spectrometry.

Two different isotope-dilution liquid chromatography/tandem mass spectrometry (LC/MS/MS) methods for the quantitative determination of folic acid (FA) in multivitamin/multielement tablets are reported. These methods represent distinct improvements in terms of speed and specificity over most existing microbiological and chromatographic methods for the determination of FA in dietary supplements. The first method utilizes an aqueous/organic-based extraction solvent combined with positive-ion mode LC/MS/MS detection of protonated [M + H]+ FA molecules and the second method utilizes a pure aqueous-based extraction solvent combined with negative-ion mode LC/MS/MS detection of deprotonated [M - H]- FA molecules. The LC/MS/MS methods exhibit comparable linear dynamic ranges (> or =3 orders of magnitude), limits of detection (0.02 ng on-column) and limits of quantification (0.06 ng on-column) for FA. Two methods employing different extraction and different MS detection modes were developed to allow method cross-validation. Successful validation of each measurement procedure supports the use of either method for the certification of FA levels in dietary supplements. The accuracy and precision of each measurement procedure were evaluated by applying each method to the quantitative determination of FA in a NIST standard reference material (NIST SRM 3280 multivitamin/multielement tablets). The FA measurement accuracy for both methods was > or =95% (based on the manufacturer's assessment of the FA level in SRM 3280) with corresponding measurement precision values (% RSD) of approximately 1%.

Chromatography, Liquid↗

PubMed2006

Analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental samples: a critical review of gas chromatographic (GC) methods.

Polycyclic aromatic hydrocarbons (PAHs) are frequently measured in the atmosphere for air quality assessment, in biological tissues for health-effects monitoring, in sediments and mollusks for environmental monitoring, and in foodstuffs for safety reasons. In contemporary analysis of these complex matrices, gas chromatography (GC), rather than liquid chromatography (LC), is often the preferred approach for separation, identification, and quantification of PAHs, largely because GC generally affords greater selectivity, resolution, and sensitivity than LC. This article reviews modern-day GC and state-of-the-art GC techniques used for the determination of PAHs in environmental samples. Standard test methods are discussed. GC separations of PAHs on a variety of capillary columns are examined, and the properties and uses of selected mass spectrometric (MS) techniques are presented. PAH literature on GC with MS techniques, including chemical ionization, ion-trap MS, time-of-flight MS (TOF-MS), and isotope-ratio mass spectrometry (IRMS), is reviewed. Enhancements to GC, for example large-volume injection, thermal desorption, fast GC, and coupling of GC to LC, are also discussed with regard to the determination of PAHs in an effort to demonstrate the vigor and robustness GC continues to achieve in the analytical sciences.

Journal Article↗

PubMed2006

Standard reference materials (SRMs) for determination of organic contaminants in environmental samples.

For the past 25 years the National Institute of Standards and Technology (NIST) has developed certified reference materials (CRMs), known as standard reference materials (SRMs), for determination of organic contaminants in environmental matrices. Assignment of certified concentrations has usually been based on combining results from two or more independent analytical methods. The first-generation environmental-matrix SRMs were issued with certified concentrations for a limited number (5 to 10) of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Improvements in the analytical certification approach significantly expanded the number and classes of contaminants determined. Environmental-matrix SRMs currently available include air and diesel particulate matter, coal tar, marine and river sediment, mussel tissue, fish oil and tissue, and human serum, with concentrations typically assigned for 50 to 90 organic contaminants, for example PAHs, nitro-substituted PAHs, PCBs, chlorinated pesticides, and polybrominated diphenyl ethers (PBDEs).

Animals↗

PubMed2006

Structure-function relationships in high-density docosylsilane bonded stationary phases by Raman spectroscopy and comparison to octadecylsilane bonded stationary phases.

Raman spectroscopy is used to investigate the effects of temperature, surface coverage, polymerization method (surface or solution polymerized), and nature of the alkylsilane precursor on alkyl chain conformational order in a series of high-density docosylsilane (C22) stationary phases at surface coverages ranging from 3.61 to 6.97 mumol/m(2). The results of this study contribute to an enhanced understanding of the shape-selective retention characteristics of these phases at a molecular level. Conformational order is evaluated using the intensity ratio of the antisymmetric and symmetric nu(CH2) modes as well as the frequency at which these modes are observed. Alkyl chain order is shown to be dependent on surface coverage, alkyl chain length, and polymerization method. In general, alkyl chain order increases with surface coverage. Temperature-induced changes are observed between 250 and 350 K for the three phases with surface coverages between 3.61 and 4.89 mumol/m(2). These changes occur over a broad range of temperatures characteristic of two-dimensional systems, but in general adhere to the behavior predicted for a simple first-order transition. This change is not believed to be an abrupt cooperative disassociation characteristic of a phase transition in a bulk phase, but instead is thought to involve significant changes in conformational order in segments of the surface-tethered molecules, mostly those segments at the outer edge of the alkylsilane. In contrast to the changes observed in coverages below 5 mumol/m(2), a first-order change is not observed for the stationary phase with coverage of 6.97 mumol/m(2). A molecular picture of the temperature-induced disorder is proposed with disorder originating at the distal carbon and propagating only a short distance toward the proximal carbon. A comparison is made between these C22 stationary phases and similar high-density octadecylsilane (C18) bonded phases.

Journal Article↗

PubMed2006

Identification of isolated cavity features within molecular dynamics simulated chromatographic surfaces.

Highly ordered morphological features were characterized for molecular dynamics simulated alkyl-modified silica models that represent chromatographic materials with enhanced shape recognition capability. Deep cavities (8-10A wide) within the alkyl chains were identified for C18 polymeric models corresponding to shape-selective RPLC stationary phases. The all-trans conformational distal-end segments of these isolated cavities averaged over a 100 ps simulation time interval were observed to increase (up to 15 A) in models with an increase in both surface coverage and corresponding shape selectivity. Similar-structure cavities with significant alkyl chain ordered regions (>11A) were isolated from two independent C18 models (differing in bonding chemistry, density and temperature) that represent highly shape-selective materials. The size and depth of these ordered regions increased (up to 28 A) for the extended-length C30 alkyl phase models. These initial results offer a physical representation of alkyl-modified surfaces that may facilitate the identification of potential molecular features that may be involved in the shape-selective retentive processes, as well as illustrating the potential for such computational techniques to predict the molecular recognition capabilities of novel analyte-specific sorbents.

Adsorption↗

PubMed2006

Development and evaluation of methods for determination of naphthodianthrones and flavonoids in St. John's wort.

Several major constituents in St. John's wort were determined for a homogenized plant sample. Three extraction techniques were evaluated: Soxhlet extraction, pressurized-fluid extraction (PFE), and sonication extraction. Levels of nine constituents (chlorogenic acid, rutin, hyperoside, isoquercitrin, quercitrin, quercetin, amentoflavone, pseudohypericin, and hypericin) were measured using liquid chromatography with ultraviolet/visible absorbance, mass spectrometric, and fluorescence detection. Levels of total naphthodianthrones determined by liquid chromatography (LC) with absorbance detection at 590 nm were compared with levels determined by direct spectrophotometry at the same wavelength. Additionally, the methods described in this paper were applied to several brands of St. John's wort finished products.

Anthracenes↗

PubMed2006

Dietary supplement Standard Reference Materials.

A new category of Standard Reference Materials (SRMs) based on dietary supplements is under development by the National Institute of Standards and Technology (NIST), with certified values for organic constituents and selected trace elements. These materials are provided primarily for use in method development and as control materials. The SRMs will assist manufacturers of dietary supplements in characterizing raw materials for potency, authenticity, and contamination or adulteration. In addition, the SRMs will assist in assessment of consistency and quality in finished products. The goal of this ongoing effort is to provide tools to the dietary supplement industry and measurement communities that will lead to improved quality of dietary supplements, and ultimately reduce public health risks that could potentially be associated with these products.

Dietary Supplements↗

PubMed2006

Conformational temperature dependence of a poly(ethylene-co-acrylic acid) stationary phase investigated by nuclear magnetic resonance spectroscopy and liquid chromatography.

A polymer-based RP sorbent was prepared by immobilizing a poly(ethylene-co-acrylic acid) copolymer with an acid mass fraction of 5% on silica by using a 3-glycidoxypropyl linkage. 13C cross-polarization/magic angle spinning NMR spectroscopy of the sorbent, either in the dry state or suspended in the mobile phase, showed an increase in mobility at elevated temperatures. Alkyl chain segments with gauche conformations were more mobile than chain segments with trans conformations. The strength of the 13C-1H dipolar couplings in the alkyl chains was measured using the constant time dipolar and chemical shift pulse sequence, revealing less molecular motion for the trans conformation. Non-linear van't Hoff plots were observed for separations of shape-constrained solutes (such as geometric beta-carotene isomers and polycyclic aromatic hydrocarbons). At higher temperatures, the retention behavior was similar to that of monomeric C18 sorbents, whereas at ambient and lower temperatures, enhanced shape-selective properties were exhibited similar to those of polymeric C30 sorbents.

Journal Article↗

PubMed2005

Molecular dynamics simulations of alkylsilane stationary-phase order and disorder. 1. Effects of surface coverage and bonding chemistry.

"Shape-selective" polymeric alkylsilane stationary phases are routinely employed over the more common monomeric phases in reversed-phase liquid chromatography (RPLC) to improve the separation of geometric isomers of shape-constrained solutes. We have investigated the molecular dynamics of chromatographic models that represent both monomeric and polymeric stationary phases with alkylsilane surface coverages and bonding chemistries typical of actual materials in an effort to elucidate the molecular-level structural features that control shape-selective separations. The structural characterization of these models is consistent with previous experimental observations of alkyl chain order and disorder: (1) alkyl chain order increases with increased surface coverage; and (2) monomeric and polymeric phases with similar surface coverages yield similar alkyl chain order (although subtle differences exist). In addition, a significant portion of the alkyl chain proximal to the silica surface is disordered (primarily gauche conformations) and the distal end is most ordered. Models that represent shape-selective RPLC phases possess a significant region of distal end chain order with primarily trans dihedral angle conformations. This is consistent with the view that the alkyl chains comprising polymeric stationary phases contain a series of well-defined and rigid voids in which shape-constrained solutes can penetrate and hence be selectively retained.

Journal Article↗

PubMed2005

Molecular dynamics simulations of alkylsilane stationary-phase order and disorder. 2. Effects of temperature and chain length.

In an effort to elucidate the molecular-level structural features that control shape-selective separations, we have investigated the molecular dynamics of chromatographic models that represent both monomeric and polymeric stationary phases with alkylsilane length and temperature conditions analogous to actual materials of low to high shape selectivity. The structural characterization of these models is consistent with previous experimental observations of alkyl chain order and disorder: alkyl chain order increases both with alkyl chain length and with reduced temperature. Models that represent shape-selective reversed-phase liquid chromatography (RPLC) phases possess a significant region of distal end chain order with primarily trans dihedral angle conformations; the extension of these ordered regions into the phase increases with an increase in chain length. Models with extended chain length (C30) possess a higher degree of conformational order and are relatively insensitive to changes in surface coverage, bonding chemistry, and temperature. Chromatography models of various chain lengths and over a temperature range that represents highly shape-selective RPLC stationary phases all contain a series of well-defined and rigid cavities; the size and depth of these "slots" increase for the C30 models, which may promote the enhanced separations of larger size shape-constrained solutes, such as carotenoids.

Journal Article↗

PubMed2005

Effect of surface coverage on the conformation and mobility of C18-modified silica gels.

C18-modified silica gels with surface coverages of 2 to 8.2 micromol m(-2), were prepared by different synthetic pathways and characterized by Fourier Transform infrared spectroscopy (FTIR), solid-state nuclear magnetic resonance (NMR) spectroscopy, and chromatographic measurements. The effects of temperature and bonding density on the conformational order of C18-modified silica gels were studied in detail by FTIR spectroscopy. The silane functionality and degree of cross-linking of silane ligands on the silica surface were evaluated by 29Si cross-polarization magic-angle spinning (CP/MAS) NMR and the structural order and mobility of the alkyl chains were investigated by 13C CP/MAS NMR spectroscopy. CH2 symmetric and anti-symmetric stretching bands and CH2 wagging bands were used as IR probes to monitor the conformational order and flexibility of the alkyl chains in the C18 phases. Qualitative information about the conformational order was obtained from frequency shifts of the CH2 symmetric and anti-symmetric stretching bands. The relative amounts of kink/gauche-trans-gauche, double-gauche, and end-gauche conformers in the alkyl chains were determined by analysis of CH2 wagging bands. These results indicate that surface coverage plays a dominant role in the conformational order of C18-modified silica gels. The FTIR and NMR data are discussed in the context of the chromatographic shape-selectivity differences.

Journal Article↗

PubMed2005

Hydrodynamic flow in capillary-channel fiber columns for liquid chromatography.

The flow characteristics of capillary-channel polymer (C-CP) fiber liquid chromatographic (LC) columns have been investigated. The C-CP fibers are manufactured with eight longitudinal grooves (capillary channels) extending the length of the fibers. Three C-CP fiber examples were studied, with fiber dimensions ranging from approximately 35 microm to 65 microm, and capillary-channel dimensions ranging from approximately 6 microm to 35 microm. The influence of fiber packing density and column inner diameter on peak asymmetry, peak width, and run-to-run reproducibility have been studied for stainless steel LC columns packed with polyester (PET) and polypropylene (PP) C-CP fibers. The van Deemter A-term was evaluated as a function of fiber packing density (approximately 0.3 g/cm(3)-0.75 g/cm(3)) for columns of 4.6 mm inner diameter (i.d.) and at constant packing densities for 1.5 mm, 3.2 mm, 4.6 mm, and 7.7 mm i.d. columns. Although column diameter had little influence on the eluting peak widths, peak asymmetry increased with increasing column diameter. The A-terms for the C-CP fiber packed columns are somewhat larger than current commercial, microparticulate-packed columns, and means for improvement are discussed. Applications in the area of protein (macromolecule) separations appear the most promising at this stage of the system development.

Chromatography, Liquid↗

PubMed2005

Determination of ephedrine alkaloid stereoisomers in dietary supplements by capillary electrophoresis.

Three complementary capillary electrophoresis (CE) methods were developed for the separation and quantification of ephedrine and pseudoephedrine stereoisomers. Either single or dual cyclodextrin-based chiral selector systems provided enantioselective separation of the compounds of interest. The three methods were applied to the analysis of a suite of five standard reference materials (SRMs) containing ephedra. Use of a high-sensitivity UV detection cell enhanced quantification of the analytes of interest over the wide range of concentrations encountered in the SRMs. Results for (-)-ephedrine ranged from 0.31 to 76.43 mg/g, and for (+)-pseudoephedrine ranged from 0.049 to 9.23 mg/g in the materials studied. Results from the three methods agreed well with each other and with the results from other methods of analysis. The addition of known amounts of specific enantiomers was used to confirm the enantiomeric identity of the analytes. The results obtained by the three CE methods were utilized for value assignment of the ephedrine alkaloid content of these five SRMs.

Alkaloids↗

PubMed2005

Determination of ephedrine alkaloids in dietary supplement standard reference materials.

A suite of five ephedra-containing dietary supplement Standard Reference Materials (SRMs) has been issued by the National Institute of Standards and Technology (NIST) with certified values for ephedrine alkaloids, synephrine, caffeine, and selected toxic trace elements. The materials represent a variety of natural, extracted, and processed sample matrixes that provide different analytical challenges. The constituents have been determined by multiple independent methods with measurements performed by NIST and by three collaborating laboratories. The methods utilized different sample extraction and cleanup steps in addition to different instrumental analytical techniques and approaches to quantification. In addition, food-matrix proximates were determined by National Food Processor Association laboratories for one of the ephedra-containing SRMs. The SRMs are primarily intended for method validation and for use as control materials to support the analysis of dietary supplements and related botanical materials.

Alkaloids↗

PubMed2005

Order and disorder in alkyl stationary phases.

Covalently modified surfaces represent a unique state of matter that is not well described by liquid or solid phase models. The chemical bond in tethered alkanes imparts order to the surface in the form of anisotropic properties that are evident in chromatographic and spectroscopic studies. An understanding of the structure, conformation, and organization of alkyl-modified surfaces is requisite to the design of improved materials and the optimal utilization of existing materials. In recent years, the study of alkyl-modified surfaces has benefited from advances in modern analytical instrumentation. Aspects of alkyl chain conformation and motion have been investigated through the use of nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, fluorescence spectroscopy, and neutron scattering studies. Chromatography provides complementary evidence of alkyl chain organization through interactions with solute probes. Computational simulations offer insights into the structure of covalently modified surfaces that may not be apparent through empirical observation. This manuscript reviews progress achieved in the study of the architecture of alkyl-modified surfaces.

Journal Article↗

PubMed2005

Reversed-phase liquid chromatography and argentation chromatography of the minor capsaicinoids.

An investigation of the liquid chromatography of the minor capsaicinoids in a commercial capsaicinoid mixture is reported. Twelve stationary phases including C8, C18, C30, phenyl, and cation-exchange chemistries were examined in combination with isocratic aqueous methanol and aqueous acetonitrile mobile phases. A phenyl stationary phase and aqueous acetonitrile mobile phase baseline-resolved 7 of 11 capsaicinoids, and selected ion chromatograms (LC-ESI-MS) demonstrated this was the most effective reversed-phase separation. Argentation chromatography with an alkyl or phenyl column and aqueous silver nitrate-methanol mobile phase revealed the presence of the 6-ene-8-methyl and 6-ene-9-methyl homocapsaicin isomers and the absence of 7-ene-9-methyl homocapsaicin. A mixed phenyl-cation-exchange stationary phase (charged with silver ion) enabled unique and useful separations of the capsaicinoids.

Capsaicin↗