High throughput liquid chromatography/mass spectrometric analyses using a novel multiplexed electrospray interface

A novel four- channel multiplexed electrospray liquid chromatography interface is described. This device has been used to analyse both single components and mixtures by liquid chromatography/mass spectrometry (LC/MS) as well as synthetic samples prepared by automated procedures. These data provided unambiguous molecular weight assignments to both major components and synthetic by-products in these samples. In this work particular attention has also been paid to the elimination of interchannel crosstalk. Copyright 1999 John Wiley & Sons, Ltd.     

Liquid chromatography/mass spectrometric determination of trans-resveratrol in wine using a tandem solid-phase extraction method

Liquid chromatography/mass spectrometry (LC/MS) with electrospray ionization has been successfully applied to the determination of trans-resveratrol (3,5,4'-trihydroxystilbene) in wine. Of a range of analytical conditions that were tested, optimum results were obtained by the use of reversed-phase high performance liquid chromatography (HPLC) using a mixture of methanol and ammonium acetate as the mobile phase. The negative-ion spectrum of trans-resveratrol showed pseudo-molecular ion, [M - H](-), which was the most abundant ion, and low fragment ions corresponding to the losses of hydroxyl groups of the phenol nucleus. Enhanced selectivity for the separation between trans-resveratrol and endogenous wine constituents was afforded by sample purification with a tandem solid-phase extraction method. The approach permits detection at low concentration of trans-resveratrol. The combination of improved sample pretreatment and an isocratic chromatographic system in conjunction with internal standardization forms the basis of a new assay for the quantitation of trans-resveratrol in wine. Full-scan mass spectra were readily obtained from 8 ng of trans-resveratrol, while a limit of detection of 200 pg (signal-to-noise ratio 3) was attained in the selected ion monitoring mode. The application of LC/MS to the determination of trans-resveratrol in wines is demonstrated by the analysis of red wines. Copyright 1999 John Wiley & Sons, Ltd.     

Thermal desorption mass spectrometric and x-ray photoelectron studies of etched surfaces of polytetrafluoroethylene

The etching of polytetrafluoroethylene (PTFE) with Na solutions is known to lead to a loss of F, a loss which is correlated with enhanced adhesion. Subsequent heating partially restores surface F with a concurrent loss of adhesion strength. We have combined X-ray photoelectron spectroscopy (XPS) and gas phase mass spectroscopy for in situ measurements of the processes that occur as the fluorocarbon is heated. An array of volatile products, which vary with the specific treatment, desorb from etched PTFE. Among these are: N₂ and low molecular weight fluorocarbons, the amounts of which monotonically decrease with increasing exposure to the etching solution (and probably result from the bulk); species such as CO and CO₂, which in part result from surface impurities; and water and acetone which result from the rinse steps following the etching process. XPS measurements show that etching produces a major loss of surface F and a gain of surface O. The latter probably results from the subsequent rinse steps. Heating produces a substantial recovery in surface F with only a small decrease in the surface O, and the gain in surface F is shown to occur at a higher temperature than the desorption of any species from the surface. Thus, desorption of products from the surface is decoupled, in terms of both the distribution of products and their relative temperatures, from the surface changes as monitored by XPS. This decoupling suggests that the increase in surface F results from diffusion of low molecular weight fluorocarbons from the bulk or a transition region, or from a rearrangement of the sponge-like surface region produced in the etching process.     

Detection of algae and bacterial biofilms formed on titanium surfaces using micro-Raman analysis

Biofouling is one of the major impediments in the use of titanium in sea-water cooled condensers of power plants, which is otherwise an excellent material with respect to corrosion resistance. Raman microscopic experiments were carried out on biofilms grown on titanium surfaces to find out the chemical composition of complex extracellular polymeric substances (EPS) in the biofilm. Though the spectral resolution of normal Raman experiments on these systems was very poor, it was improved when micro-SERS experiments were carried out using mono and bimetallic Ag and Cu colloids. It was observed that spatial distribution of polysaccharides was higher than that of proteins in algae biofilms formed on titanium matrix. Similar experiments were performed on laboratory cultured bacterial films of Pseudomonas aeruginosa. It was evidenced that algal and bacterial biofilms on titanium can be clearly distinguished with the help of Raman mapping coupled with SERS technique using bimetallic Ag/Cu colloids.     

Analytical treatment of light extraction from textured surfaces using classical ray optics

Regular periodic textures e.g., microlens arrays, micro-pyramids, and cones on substrate surface have been used to enhance light out-coupling in light emitting devices. Photon randomization, often associated with surface roughening, has been suggested as the mechanism for out-coupling enhancement. This article analytically investigates the ray dynamics in a light emitting device when periodic texture is used as an external out-coupler. An attempt has been made to understand the relationship between enhancement in out-coupling and the surface inclination of these structures using classical ray optics.     

Supercritical fluid extraction of pesticides from human hair followed by gas chromatography-mass spectrometric analysis

A supercritical fluid extraction process using supercritical carbon dioxide for the isolation of chlororganic and phosphororganic pesticides from human hair is developed. The effect of process parameters (temperature, pressure, duration) on the efficiency of pesticide extraction is studied. The gas chromatography-mass spectrometry technique is used for the quantitative analysis of pesticide concentration in hair.     

Direct observation of surface diffusion and atomic interactions on metal surfaces

The unique attributes of the field ion microscope permit the direct observation of surface diffusion of single atoms and simple atomic clusters on perfect crystal planes. A brief review of the principles and techniques of such studies is presented along with a collection of much of the existing experimental data. Emphasis is placed on more recent work such as the diffusion of adatoms under the influence of a driving force, the kinetics of cluster formation and dissociation, and how the interatomic force between two atoms on a surface is related to the diffusion parameters and the pair distribution function.     

Temperature-dependent evolution of surface charge screening and polarization at ferroelectric surfaces

<正>The polarization and domain behavior on the surface of a ferroelectric material are significantly affected by the screening processes [1-12]. Recently, there has been a notable increase in the theoretical calculations and experiments investigating the dynamics of polarization and domain behaviors coexisting in phase transitions of ferroelectric materials. There is thus a widespread interest in the dynamics of the screening charges on ferroelectric surfaces [8-14]. On the other hand, BaTiO_3(BTO), has attracted the attention as it     

Electrospray ionization multiple-stage tandem mass spectrometric analysis of diglycosyldiacylglycerol glycolipids from the bacteria Bacillus pumilus

Electrospray ionization (ESI) combined with multiple-stage tandem mass spectrometry (MS(n)) was used to directly analyze the glycolipid mixture from bacteria Bacillus pumilus without preliminary separation. Full scan ESI-MS revealed the composition of picomole quantities of glycerolglycolipid species containing C(14)-C(19) fatty acids, some of which were monounsaturated. Two main components were identified from their molecular masses and fragmentation pathways. The fragmentation pathway of the known compound compared with the investigated compound verified the proposed structure as 1(3)-acyl-2-pentadecanoyl-3(1)-O-[beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl]-sn-glycerols. A comparison of the multiple tandem mass spectra of the different alkali-metal cation adducts indicates that the intensity of fragments and the dissociation pathways are dependent on the alkali-metal type. The basic structures of glycerolglycolipids were reflected clearly from the fragmentation patterns of the sodium cations. The intense fragments of the sugar residue from the precursor ions were obtained from the lithiated adduct ions. ESI-MS(n) spectra of [M + K](+) ions did not provide as much fragmentation as [M + Na](+) and [M + Li](+) adducts, but their spectra allow the position of glycerol acylation to be determined. On the basis of MS(2) spectra of [M + K](+) ions, it was established that all components have a C(15:0) fatty acid at the sn-2 position of the glycerol backbone and C(14)-C(19) acids at the sn-1 position of the glycerol backbone. Copyright 1999 John Wiley & Sons, Ltd.     

Direct mass measurements of neutron-deficient xenon isotopes using the ISOLTRAP mass spectrometer

The masses of the noble-gas Xe isotopes with have been directly measured for the first time. The experiments were carried out with the ISOLTRAP triple trap spectrometer at the on-line mass separator ISOLDE/CERN. A mass resolving power of the Penning trap spectrometer of of close to a million was chosen resulting in an accuracy of keV for all investigated isotopes. Conflicts with existing, indirectly obtained, mass data by several standard deviations were found and are discussed. An atomic mass evaluation has been performed and the results are compared to information from laser spectroscopy experiments and to recent calculations employing an interacting boson model.PACS: 07.75. + h Mass spectrometers - 21.10.Dr Binding energies and masses - 27.60. + j - 32.10.Bi Atomic masses, mass spectra, abundances, and isotopes     

Direct observation of terahertz surface modes in nanometer-sized liquid water pools

The far-infrared absorption spectrum of nanometer-sized water pools at the core of AOT micelles exhibits a pronounced resonance which is absent in bulk water. The amplitude and spectral position of this resonance are sensitive to the size of the confined water core. This resonance results from size-dependent modifications in the vibrational density of states, and thus has far-reaching implications for chemical processes which involve water sequestered within small cavities. These data represent the first study of the terahertz dielectric properties of confined liquids.     

Temperature dependence of surface tension and capillary waves at liquid metal surfaces

The temperature dependence of the surface tension γ(T) is treated theoretically and experimentally. The theoretical model based on the Gibbs thermodynamics of a one-component fluid relates ∂γ/∂T to the surface excess entropy density −ΔS. All specific surface effects, namely ordering, capillary waves, and double layer influence the surface entropy, which in turn governs the sign and the magnitude of ∂γ/∂T. Experimental data collected at a free Hg surface in the temperature range from 0°C to 30°C show that ∂γ/∂T is negative. Zh. éksp. Teor. Fiz. 114, 2034–2042 (December 1998) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

Optimization of ultrasonic-assisted extraction of natural antioxidants from rice bran using response surface methodology

Ultrasonic technology was applied for extraction of polyphenols and antioxidants from the rice bran using ethanol as a food grade solvent. Response surface methodology (RSM) was used to optimize experimental conditions for extraction of polyphenols and antioxidants. Three independent variables such as solvent percentage (%), temperature (°C) and time (min) were studied. Effect of ethanol concentration was found to be significant on all responses. Total phenolic content (TPC) varied from 2.37 to 6.35mg gallic acid equivalent/g of dry sample. Antioxidant activity of the extracts was determined by the ferric reducing antioxidant power (FRAP) assay and scavenging activity of 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical. FRAP and DPPH values varied from 31.74 to 57.23μmol Fe(2+)/g of dry sample and 16.88% to 55.61% inhibition, respectively. Extraction yields ranged from 11 to 20.2%. Optimal ultrasonic-assisted extraction (UAE) conditions were identified as 65-67% ethanol, 51-54°C, 40-45min. The experimental values agreed with those predicted by SRM models, thus indicating suitability of the model employed and the success of RSM in optimizing the extraction conditions.     

Optimization of ultrasonic cell grinder extraction of anthocyanins from blueberry using response surface methodology

Ultrasonic cell grinder extraction (UCGE), using water as the solvent, was firstly applied to extract anthocyanins from blueberry. Extraction yield was related with four variables, including ratio of solution to solid, extraction power, buffer time, and extraction time. On the basis of response surface methodology (RSM), the optimal conditions were determined to be the ratio of solution to solid as 25:1 (mL/g), the extraction power as 1500 W, the buffer time as 3.0 s, and the extraction time as 40 min. The experimental yield of anthocyanins using UCGE was 2.89 mg/g higher than that of conventional ultrasound-assisted extraction (CUAE). This study indicated that UCGE was an innovative, efficient, and environment friendly method in ultrasonic extraction fields, and had a potential to effectively extract other bioactive constituents.