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1.
Appl Opt ; 60(8): 2288-2303, 2021 Mar 10.
Article in English | MEDLINE | ID: mdl-33690328

ABSTRACT

The advanced radiographic capability (ARC) laser system, part of the National Ignition Facility (NIF) at Lawrence Livermore National Laboratory, is a short-pulse laser capability integrated into the NIF. The ARC is designed to provide adjustable pulse lengths of ∼1-38ps in four independent beamlets, each with energies up to 1 kJ (depending on pulse duration). A detailed model of the ARC lasers has been developed that predicts the time- and space-resolved focal spots on target for each shot. Measurements made to characterize static and dynamic wavefront characteristics of the ARC are important inputs to the code. Modeling has been validated with measurements of the time-integrated focal spot at the target chamber center (TCC) at low power, and the space-integrated pulse duration at high power, using currently available diagnostics. These simulations indicate that each of the four ARC beamlets achieves a peak intensity on target of up to a few 1018W/cm2.

2.
Appl Opt ; 52(20): 5030-5, 2013 Jul 10.
Article in English | MEDLINE | ID: mdl-23852219

ABSTRACT

A standard technique for beam propagation modeling of large and complex optical systems, such as the National Ignition Facility, is the Talanov approach. We describe a modification to the Talanov algorithm that avoids its inherent inability to treat interactions in the Rayleigh region. The algorithm has been validated with analytic and numerical calculations and is demonstrated to function as expected in the case of a NIF spatial filter.

3.
J Emerg Med ; 42(3): 275-8, 2012 Mar.
Article in English | MEDLINE | ID: mdl-19201139

ABSTRACT

BACKGROUND: Dog bites are the most common animal bite injuries occurring in the United States. Estimated infection rates range between 15% and 20%. Polymicrobial infections are most common. Capnocytophaga canimorsus (C. canimorsus) is a Gram-negative rod strongly associated with dog bites, and is known to cause life-threatening infection in humans. OBJECTIVES: 1) Outline epidemiology of dog bites in the United States; 2) Identify host factors associated with infection, and common pathogens; 3) Discuss microbiology of C. canimorsus; 4) Discuss common clinical manifestations of C. canimorsus infection; 5) Outline treatment options. CASE REPORT: A 42-year-old woman with a remote history of Hodgkin's lymphoma (treated with irradiation) and thyroid carcinoma, both of which were in remission, presented to the Emergency Department with fever, abdominal pain, and diarrhea. She was found to be in septic shock. She was aggressively resuscitated and administered broad-spectrum antibiotics. Blood cultures grew C. canimorsus in 2/4 bottles. The patient recalled being bitten by the family dog 48 h before her initial presentation. She made an uneventful recovery. She was felt to be "functionally hyposplenic" due to her prior irradiation. CONCLUSIONS: C. canimorsus is a rare pathogen strongly associated with dog bites. By eliciting a history of animal bite, clinicians may be able to alert the laboratory of suspected C. canimorsus infection. Prolonged laboratory incubation times may be necessary as the organism is fastidious. Predisposing conditions include, among others, prior splenectomy and alcoholism. The mortality rate from C. canimorsus sepsis is high, so treatment should be promptly initiated.


Subject(s)
Bites and Stings/complications , Capnocytophaga/isolation & purification , Dogs , Gram-Negative Bacterial Infections/diagnosis , Shock, Septic/microbiology , Adult , Animals , Bites and Stings/microbiology , Female , Gram-Negative Bacterial Infections/microbiology , Humans
4.
Am J Physiol Lung Cell Mol Physiol ; 296(6): L870-8, 2009 Jun.
Article in English | MEDLINE | ID: mdl-19286928

ABSTRACT

Chronic thromboembolic pulmonary hypertension (CTEPH) is characterized by a fibrotic thrombus persisting and obliterating the lumen of pulmonary arteries; its pathogenesis remains poorly defined. This study investigates a potential contribution for progenitor cell types in the development of vascular obliteration and remodeling in CTEPH patients. Endarterectomized tissue from patients undergoing pulmonary thromboendarterectomy was collected and examined for the structure and cellular composition. Our data show an organized fibrin network structure in unresolved thromboemboli and intimal remodeling in vascular wall tissues, characterized by smooth muscle alpha-actin (SM-alphaA)-positive cell proliferation in proximal regions (adjacent to thromboemboli) and neoangiogenesis/recanalization in distal regions (downstream from thromboemboli). Cells that are positively stained with CD34 and fetal liver kinase-1 (Flk-1) (CD34(+)Flk-1(+)) were identified in both the proximal and distal vascular tissues; a subpopulation of CD34(+)Flk-1(+)CD133(+) cells were further identified by immunostaining. Triple-positive cells are indicative of a population of putative endothelial progenitor cells or potential colony-forming units of endothelial cells. In addition, inflammatory cells (CD45(+)) and collagen-secreting cells (procollagen-1(+)) were detected in the proximal vascular wall. Some of the CD34(+) cells in CTEPH cells isolated from proximal regions were also positive for SM-alphaA. Our data indicate that putative progenitor cell types are present in the neointima of occluded vessels of CTEPH patients. It is possible that the microenvironment provided by thromboemboli may promote these putative progenitor cells to differentiate and enhance intimal remodeling.


Subject(s)
Endothelium, Vascular/cytology , Hypertension, Pulmonary/pathology , Mesenchymal Stem Cells/cytology , Pulmonary Artery/pathology , Pulmonary Embolism/pathology , AC133 Antigen , Antigens, CD/genetics , Antigens, CD/metabolism , Antigens, CD34/genetics , Antigens, CD34/metabolism , Cell Differentiation/physiology , Cells, Cultured , Chronic Disease , Endarterectomy , Endothelial Cells/cytology , Glycoproteins/genetics , Glycoproteins/metabolism , Humans , Hypertension, Pulmonary/metabolism , Hypertension, Pulmonary/surgery , Mesenchymal Stem Cells/metabolism , Peptides/genetics , Peptides/metabolism , Pulmonary Artery/metabolism , Pulmonary Artery/surgery , Pulmonary Embolism/metabolism , Pulmonary Embolism/surgery , Reverse Transcriptase Polymerase Chain Reaction , Vascular Endothelial Growth Factor Receptor-2/genetics , Vascular Endothelial Growth Factor Receptor-2/metabolism
5.
Am J Physiol Lung Cell Mol Physiol ; 295(6): L1048-55, 2008 Dec.
Article in English | MEDLINE | ID: mdl-18836030

ABSTRACT

Thrombin is a procoagulant inflammatory agonist that can disrupt the endothelium-lumen barrier in the lung by causing contraction of endothelial cells and promote pulmonary cell proliferation. Both contraction and proliferation require increases in cytosolic Ca(2+) concentration ([Ca(2+)](cyt)). In this study, we compared the effect of thrombin on Ca(2+) signaling in human pulmonary artery smooth muscle (PASMC) and endothelial (PAEC) cells. Thrombin increased the [Ca(2+)](cyt) in both cell types; however, the transient response was significantly higher and recovered quicker in the PASMC, suggesting different mechanisms may contribute to thrombin-mediated increases in [Ca(2+)](cyt) in these cell types. Depletion of intracellular stores with cyclopiazonic acid (CPA) in the absence of extracellular Ca(2+) induced calcium transients representative of those observed in response to thrombin in both cell types. Interestingly, CPA pretreatment significantly attenuated thrombin-induced Ca(2+) release in PASMC; this attenuation was not apparent in PAEC, indicating that a PAEC-specific mechanism was targeted by thrombin. Treatment with a combination of CPA, caffeine, and ryanodine also failed to abolish the thrombin-induced Ca(2+) transient in PAEC. Notably, thrombin-induced receptor-mediated calcium influx was still observed in PASMC after CPA pretreatment in the presence of extracellular Ca(2+). Ca(2+) oscillations were triggered by thrombin in PASMC resulting from a balance of extracellular Ca(2+) influx and Ca(2+) reuptake by the sarcoplasmic reticulum. The data show that thrombin induces increases in intracellular calcium in PASMC and PAEC with a distinct CPA-, caffeine-, and ryanodine-insensitive release existing only in PAEC. Furthermore, a dynamic balance between Ca(2+) influx, intracellular Ca(2+) release, and reuptake underlie the Ca(2+) transients evoked by thrombin in some PASMC. Understanding of such mechanisms will provide an important insight into thrombin-mediated vascular injury during hypertension.


Subject(s)
Calcium Signaling/drug effects , Calcium/metabolism , Endothelial Cells/metabolism , Muscle, Smooth, Vascular/metabolism , Pulmonary Artery/metabolism , Thrombin/pharmacology , Biological Clocks/drug effects , Biological Clocks/physiology , Caffeine/pharmacology , Calcium Signaling/physiology , Endothelial Cells/cytology , Humans , Indoles/pharmacology , Muscle, Smooth, Vascular/cytology , Organ Specificity/physiology , Phosphodiesterase Inhibitors/pharmacology , Pulmonary Artery/cytology , Ryanodine/pharmacology , Sarcoplasmic Reticulum/metabolism , Thrombin/metabolism
6.
J Sep Sci ; 30(7): 1052-60, 2007 May.
Article in English | MEDLINE | ID: mdl-17566340

ABSTRACT

The performance characteristics of a portable GC instrument requiring no compressed gas supplies and using relatively lightweight transportable components for the analysis of volatile organic components in large-volume air samples are described. To avoid the need for compressed gas tanks, ambient air is used as the carrier gas, and a vacuum pump is used to pull the carrier gas and injected samples through the wall-coated capillary column and a photoionization detector (PID). At-column heating is used eliminating the need for a conventional oven. The fused silica column is wrapped with heater wire and sensor wire so that heating is provided directly at the column. A PID is used since it requires no external gas supplies and has high sensitivity for many compounds of interest in environmental air monitoring. In order to achieve detection limits in the ppb range, an online multibed preconcentrator containing beds of graphitized carbons and carbon molecular sieves is used. After sample collection, the flow direction through the preconcentrator is reversed, and the sample is thermally desorbed directly into the column. Decomposition of sensitive compounds during desorption is greater with air as the carrier gas than with hydrogen.


Subject(s)
Breath Tests , Organic Chemicals/analysis , Air , Breath Tests/instrumentation , Breath Tests/methods , Chromatography, Gas/instrumentation , Chromatography, Gas/methods , Gases/chemistry , Humans , Reference Values , Sensitivity and Specificity , Silicon Dioxide/chemistry , Time Factors
7.
Anal Chem ; 79(7): 2911-7, 2007 Apr 01.
Article in English | MEDLINE | ID: mdl-17311465

ABSTRACT

Columns were fabricated in silicon substrates by deep reactive-ion etching. The channels were sealed with a glass wafer anodically bonded to the silicon surface. Heaters and temperature sensors were fabricated on the back side of each column chip. A microcontroller-based temperature controller was used with a PC for temperature programming. Temperature programming, with channel lengths of 3.0 and 0.25 m, is described. The 3.0-m-long channel was fabricated on a 3.2 cmx3.2 cm chip. Four columns were fabricated on a standard 4-in. silicon wafer. The 0.25-m-long channel was fabricated on a 1.1 cmx1.1 cm chip, and approximately 40 columns could be fabricated on a 4-in. wafer. All columns were coated with a nonpolar poly(dimethylsiloxanes) stationary phase. A static coating procedure was employed. The 3.0-m-long column generated about 12000 theoretical plates, and the 0.25-m-long channel generated about 1000 plates at optimal carrier gas velocity. Linear temperature ramps as high as 1000 degrees C/min when temperature programmed from 30 to 200 degrees C were obtained with the shorter column. With the 0.25-m-long column, normal alkanes from n-C5 through n-C15 were eluted in less than 12 s using a temperature ramp rate of 1000 degrees C/min. Temperature uniformity over the column chip surface was measured with infrared imaging. A variation of about 2 degrees C was obtained for the 3.0-m-long channel. Retention time reproducibility with temperature programming typically ranged from +/-0.15% to +/-1.5%. Design of the columns and the temperature controller are discussed. Performance data are presented for the different columns lengths.


Subject(s)
Heating/instrumentation , Silicon/chemistry , Temperature , Chromatography, Gas/instrumentation , Chromatography, Gas/methods , Electrodes , Equipment Design , Heating/methods , Sensitivity and Specificity , Time Factors
8.
Semin Thorac Cardiovasc Surg ; 18(3): 265-76, 2006.
Article in English | MEDLINE | ID: mdl-17185190

ABSTRACT

Recent efforts have seen major advances in elucidating the mechanisms underlying pulmonary arterial hypertension. However, chronic thromboembolic pulmonary hypertension (CTEPH) often has been excluded from these studies. Consequently, whereas the clinical, radiographic, and hemodynamic characteristics of CTEPH have been well described, there remains a deficit in our understanding of the cellular, molecular, and genetic mechanisms underlying CTEPH. Furthermore, although prior venous thromboembolism may act as the inciting event, it is still unclear what predisposes some patients to develop CTEPH. CTEPH has two major pathogenic components. The first is the primary obstruction of central pulmonary arteries by accumulation of thrombotic material. The second is characterized by severe pulmonary vascular remodeling, similar to that seen in idiopathic pulmonary arterial hypertension. Other articles in this series describe the pathological, surgical, and therapeutic aspects of CTEPH. Here, we review the potential molecular and cellular mechanisms that may contribute to the pathogenesis of CTEPH.


Subject(s)
Hypertension, Pulmonary/physiopathology , Molecular Biology , Pulmonary Embolism/physiopathology , Chronic Disease , Disease Susceptibility , Endothelium/physiopathology , Humans , Hypertension, Pulmonary/genetics , Platelet Aggregation , Pulmonary Embolism/genetics
9.
J Chromatogr A ; 1135(2): 230-40, 2006 Dec 01.
Article in English | MEDLINE | ID: mdl-17064715

ABSTRACT

Fast GC separations of a broad range of analytes are demonstrated using a capillary column coated with a novel immobilized ionic liquid (IIL) stationary phase. Both completely cross-linked and partially cross-linked columns were evaluated, yielding approximately 1600 and approximately 2000 theoretical plates per meter, respectively. Enhanced separation is demonstrated using a dual-column ensemble comprised of an IIL column, a commercially coated Rtx-1 column, and a pneumatic valve connecting the inlet to the junction point between the two columns. Enhanced separation of 20 components, with two sets of co-eluting peaks is shown in approximately 150 s, while sacrificing only a length of time equivalent to the sum of the stop flow pulses, or about 15.5 s. A novel application of a band trajectory model that shows band position as a function of analysis time as analytes move through the column ensemble is employed to determine pulse application times. The model predicts component retention times within a few seconds. Another method of selectivity enhancement of the IIL stationary phase-coated columns is demonstrated using a differential mobility spectrometer (DMS) that provides a second dimension separation based on ion mobility in a high-frequency electrical field. The DMS is able to separate all but one set of co-eluting components from the IIL column. The separation of 13 components found in the headspace above U.S. currency is demonstrated using the IIL column in a dual-column ensemble as well as with the DMS.


Subject(s)
Chromatography, Gas/methods , Spectrum Analysis/methods , Models, Theoretical
10.
Anal Chem ; 78(19): 6765-73, 2006 Oct 01.
Article in English | MEDLINE | ID: mdl-17007495

ABSTRACT

A microcountercurrent flame photometric detector (microcc-FPD) was adapted and optimized for ultrafast gas chromatographic (GC) separation and detection of organophosphor (OP) and organosulfur (OS) compounds on short chromatographic columns. Air and hydrogen are introduced to the microcc-FPD from opposite directions, creating a hydrogen-rich flame. In this microcc-FPD, combustion takes place between the burner tips without touching them. The separation between the tips and the flame reduces heat loss from the flame to the surrounding environment, resulting in low hydrogen consumption and a compact flame. The microcc-FPD is capable of detecting very narrow (13 ms) chromatographic peaks. An ultrafast GC separation of a group of six OP and OS compounds is achieved within less than 5 s using fast temperature programming of a 0.5-m-long microbore column. Very fast separations are also demonstrated on a 1-m-long microfabricated column consisting of 150-microm-wide, 240-microm-deep channels, etched in a 1.9-cm square silicon chip, covered with a Pyrex wafer, and statically coated with dimethyl polysiloxane. With a hydrogen flow rate of 10 mL/min, the detection limit for OP is 12 pg of P/s and 3 ng of S/s for OS compounds at a signal-to-noise ratio of 2. The coupling of a microfabricated column and a miniature FPD is an important step toward the development of a miniaturized GC-FPD capable of ultrafast detection of low levels of OP and OS compounds.

11.
J Chromatogr A ; 1132(1-2): 280-8, 2006 Nov 03.
Article in English | MEDLINE | ID: mdl-16934276

ABSTRACT

The reddish brown haze that surrounds Titan, Saturn's largest moon, is thought to consist of tholin-like organic aerosols. Tholins are complex materials of largely unknown structure. The very high peak capacity and structured chromatograms obtained from comprehensive two-dimensional GC (GC x GC) are attractive attributes for the characterization of tholin pyrolysis products. In this report, GC x GC with time-of-flight MS detection and a flash pyrolysis inlet is used to characterize tholin pyrolysis products. Identified pyrolysis products include low-molecular-weight nitriles, alkyl substituted pyrroles, linear and branched hydrocarbons, alkyl-substituted benzenes and PAH compounds. The pyrolysis of standards found in tholin pyrolysate showed that little alteration occurred and thus these structures are likely present in the tholin material.


Subject(s)
Chromatography, Gas/methods , Extraterrestrial Environment/chemistry , Mass Spectrometry/methods , Aerosols/analysis , Chromatography, Gas/instrumentation , Mass Spectrometry/instrumentation , Molecular Structure , Organic Chemicals/analysis , Saturn
12.
J Sep Sci ; 29(7): 1001-8, 2006 May.
Article in English | MEDLINE | ID: mdl-16833233

ABSTRACT

A transportable GC x GC instrument is under development for on-site applications that would benefit from the enhanced resolution and powers of detection, which can be achieved by this method. In the present study, a low-resource GC x GC instrument using an electrically heated and liquid-cooled single-stage thermal modulator that requires no cryogenic materials is evaluated. The instrument also uses at-column heating, thus eliminating the need for a convection oven to house the two columns. The stainless-steel modulator tube is coated with PDMS, which can be heated to 350 degrees C for sample injection into the second-dimension column. The modulator is cooled to -30 degrees C by a 100 mL/min flow of PEG by means of a commercial liquid chiller and a small recirculating pump. Resistive heating of the modulator tube is provided by a programmable power supply, which uses a voltage program that results in increasing modulator temperature during an analysis. This, together with more rapid cooling by the use of a liquid cooling medium, results in reduced solute breakthrough following each heating cycle as the modulator cools to a temperature where quantitative trapping resumes. As a result, modulated peak widths at half-height of less than 40 ms are observed. Design and performance details are presented along with chromatograms of gasoline and an essential oil sample.

13.
Article in English | MEDLINE | ID: mdl-16765110

ABSTRACT

A multi-bed sorption trap designed to quantitatively collect volatile organic compounds from large-volume vapor samples and inject them into a gas chromatograph is combined with a comprehensive two-dimensional gas chromatograph (GCxGC) for the analysis of organic compounds in human breath samples. The first-column effluent of the GCxGC is modulated by a single-stage, resistively-heated and air-cooled segment of 0.18-mm i.d. stainless steel column using the same stationary phase as the first column. Cooling gas is provided by a two-stage conventional refrigeration system, and thus no consumables other than carrier gas and electric power are required. The sorption trap uses four discreet beds, three containing different grades of graphitized carbon and one containing a carbon molecular sieve. The ordering of the beds in the trap tube is from the weakest to strongest adsorbent during sample collection. Breath samples are collected in gas sampling bags, and samples are passed through the trap at a flow rate of about 50 cm3/min. After sample collection, hydrogen carrier gas flow is initiated in the direction opposite to the sample collection flow, and the metal trap tube is resistively heated to inject a sample plug into the GCxGC. Performance data for the combined GCxGC/sorption-trap instrument is described, and human breath-sample chromatograms are presented.


Subject(s)
Breath Tests , Chromatography, Gas/methods , Carbon , Humans
14.
Anal Chem ; 78(8): 2623-30, 2006 Apr 15.
Article in English | MEDLINE | ID: mdl-16615772

ABSTRACT

A procedure is described for the preparation of high-performance etched silicon columns for gas chromatography. Rectangular channels, 150 mum wide by 240 mum deep are fabricated in silicon substrates by gas-phase reactive ion etching. A 0.1-0.2-mum-thick film of dimethyl polysiloxane stationary phase is deposited on the channel walls by filling the channel with a dilute solution in 1:1 n-pentane and dichloromethane and pumping away the solvent. A thermally activated cross-linking agent is used for in situ cross-linking. A 3-m-long microfabricated column generated approximately 12 500 theoretical plates at optimal operating conditions using air as carrier gas. A kinetic model for the efficiency of rectangular cross-section columns is used to evaluate column performance. Results indicate an additional source of gas-phase dispersion beyond longitudinal diffusion and nonequilibrium effects, probably resulting from numerous turns in the gas flow path through the channel. The columns are thermally stable to at least 180 degrees C using air carrier gas. Temperature programming is demonstrated for the boiling point range from n-C5 to n-C12. A 3.0-m-long column heated at 10 degrees C/min obtains a peak capacity of over 100 peaks with a resolution of 1.18 and a separation time of approximately 500 s. With a 0.25-m-long column heated at 30 degrees C/min, a peak capacity of 28 peaks is obtained with a separation time of 150 s. Applications are shown for the analysis of air-phase petroleum hydrocarbons and the high-speed analysis of chemical warfare agent and explosive markers.


Subject(s)
Air Pollutants/analysis , Chromatography, Gas/methods , Silicon/chemistry , Solvents/chemistry , Chemical Warfare Agents/analysis , Chromatography, Gas/instrumentation , Cross-Linking Reagents/chemistry , Dimethylpolysiloxanes/chemistry , Explosive Agents/analysis , Hydrocarbons/analysis , Methylene Chloride/chemistry , Pentanes/chemistry , Petroleum/analysis , Reproducibility of Results , Sensitivity and Specificity , Temperature , Time Factors
15.
Anal Chem ; 78(9): 3046-54, 2006 May 01.
Article in English | MEDLINE | ID: mdl-16642992

ABSTRACT

A method for the determination of volatile organic compounds (VOCs) at sub-trace levels in breath samples based on a multibed sorption trap for the collection and concentration of VOCs, a comprehensive multidimensional gas chromatograph (GCxGC) for the separation of complex mixtures, and a time-of-flight mass spectrometer detector is designed and developed. The good performance of the trap tube device developed for the concentration together with the high sensitivity and separation power of the GCxGC results in a powerful system. In the analysis of samples, more than 100 different compounds are detected of which between 65 and 85 are clearly identified. A total of approximately 250 different compounds are observed in all the samples evaluated of which 142 are identified. A preliminary study to evaluate breath biomarkers for active smoking is performed. The levels of previously described biomarkers are found to be strongly time-dependent with amounts found approximately 1 h after smoking returning to the levels found in nonsmoking volunteers. However, 2,5-dimethylfuran, 2-methylfuran, and furan are found to be effective biomarkers given that they were only found in samples taken from smokers and could still be detected more than 2 h after smoking.


Subject(s)
Organic Chemicals/analysis , Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization/methods , Adsorption , Breath Tests/instrumentation , Chromatography, Gas/methods , Humans , Sensitivity and Specificity , Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization/instrumentation , Time Factors
16.
J Sep Sci ; 29(2): 218-27, 2006 Feb.
Article in English | MEDLINE | ID: mdl-16524095

ABSTRACT

The effects of split-flow operation and rapid trap heating on injection-plug widths from an electrically heated, microscale, multibed sorption trap were evaluated. The sorption trap has been designed to quantitatively collect volatile organic compounds from large-volume vapor samples and inject them into a gas chromatograph. Previous trap designs resulted in injection-plug widths of typically a second or more, and this significantly degraded chromatographic resolution, particularly for early-eluting sample components and for high-speed separations. Injection-plug widths are determined by the heating rate of the trap during sample desorption and the volumetric flow rate of carrier gas through the trap. The effects of the heating rate of the trap and carrier gas velocity through the trap on the injection-plug widths of pentane, octane, and undecane were studied. Carrier gas velocity through the trap was increased by splitting the flow coming from the trap between the column and a vent. This decreases transport time from the trap to the column, and thus decreases injection-plug widths. The heating rate for the trap was increased by increasing the applied voltage in the range from 4 to 30 V. Increasing the heating rate decreases the time required to desorb the analytes from the sorbent bed, thus decreasing injection-plug width. Injection-plug widths as small as 89, 210, and 520 ms were obtained in the split mode with very fast heating rates for n-pentane, noctane, and n-undecane, respectively. The effect of split ratio on resolving power, peak height, and peak width was also evaluated.


Subject(s)
Air/analysis , Chromatography, Gas/methods , Chromatography, Gas/instrumentation , Flame Ionization/instrumentation , Flame Ionization/methods , Hot Temperature , Organic Chemicals/analysis , Volatilization
17.
Anal Chem ; 77(23): 7563-71, 2005 Dec 01.
Article in English | MEDLINE | ID: mdl-16316163

ABSTRACT

A 3.0-m-long, 150-microm-wide, 240-microm-deep channel etched in a 3.2-cm-square silicon chip, covered with a Pyrex wafer, and coated with a dimethyl polysiloxane stationary phase is used for the GC separation of volatile organic compounds. The column, which generates approximately 5500 theoretical plates, is temperature-programmed in a conventional convection oven. The column is connected through a heated transfer line to a microfabricated differential mobility spectrometer. The spectrometer incorporates a 63Ni source for atmospheric-pressure chemical ionization of the analytes. Nitrogen or air transport gas (flow 300 cm(3)/min) drives the analyte ions through the cell. The spectrometer operates with an asymmetric radio frequency (RF) electric field between a pair of electrodes in the detector cell. During each radio frequency cycle, the ion mobility alternates between a high-field and a low-field value (differential mobility). Ions oscillate between the electrodes, and only ions with an appropriate differential mobility reach a pair of biased collectors at the downstream end of the cell. A compensation voltage applied to one of the RF electrodes is scanned to allow ions with different differential mobilities to pass through the cell without being annihilated at the RF electrodes. A unique feature of the device is that both positive and negative ions are detected from a single experiment. The combined microfabricated column and detector is evaluated for the analysis of volatile organic compounds with a variety of functionalities.


Subject(s)
Chromatography, Gas/instrumentation , Chromatography, Gas/methods , Organic Chemicals/chemistry , Silicon/chemistry , Temperature , Volatilization
18.
Lab Chip ; 5(10): 1123-31, 2005 Oct.
Article in English | MEDLINE | ID: mdl-16175269

ABSTRACT

The fabrication, assembly, and initial testing of a hybrid microfabricated gas chromatograph (microGC) is described. The microGC incorporates capabilities for on-board calibration, sample preconcentration and focused thermal desorption, temperature-programmed separations, and "spectral" detection with an integrated array of microsensors, and is designed for rapid determinations of complex mixtures of environmental contaminants at trace concentrations. Ambient air is used as the carrier gas to avoid the need for on-board gas supplies. The microsystem is plumbed through an etched-Si/glass microfluidic interconnection substrate with fused silica capillaries and employs a miniature commercial pump and valve subsystem for directing sample flow. The latest performance data on each system component are presented followed by first analytical results from the working microsystem. Tradeoffs in system performance as a function of volumetric flow rate are explored. The determination of an 11-vapor mixture of typical indoor air contaminants in less than 90 s is demonstrated with projected detection limits in the low part-per-billion concentration range for a preconcentrated air-sample volume of 0.25 L.


Subject(s)
Chromatography, Gas/instrumentation , Microfluidic Analytical Techniques/instrumentation , Air , Air Pollutants/analysis , Calibration , Chromatography , Chromatography, Gas/methods , Electrophoresis, Capillary/methods , Environmental Monitoring/methods , Glass , Hot Temperature , Microfluidic Analytical Techniques/methods , Silicon/chemistry , Temperature , Time Factors
19.
J Chromatogr A ; 1086(1-2): 151-9, 2005 Sep 09.
Article in English | MEDLINE | ID: mdl-16130667

ABSTRACT

An electrically heated and air cooled metal sheath surrounding the first 50 cm of the second column in a series-coupled, capillary-column ensemble of a non-polar and a polar column is used to obtain enhanced isothermal separation of component pairs that are separated by the first column in the ensemble but co-elute from the ensemble by virtue of the different selectivity of the two columns. As the first of the two components passes into the second column, a current pulsed through the metal sheath rapidly heats the first 50 cm of the second column thus accelerating the band for the first component. Ensemble retention-time shifts of several seconds are easily obtained. The device is then rapidly cooled to quiescent oven temperature by a flow of pressured air through the space between the metal sheath and the fused silica capillary column and an additional flow through a larger, co-axial plastic tube. Both heating and cooling require only a few seconds. If substantial cooling of the device occurs before the band for the second component enters the device, the band experiences less thermally-induced acceleration with the result that the separation of the two targeted components is enhanced in the ensemble chromatogram with no significant change in the pattern of peaks for the other mixture components. If the device is cooled to a temperature below oven temperature before the arrival of the band for the second component, this band will be slowed, and further enhancement of separation is achieved in the ensemble chromatogram. A band trajectory model, based on retention factor versus temperature data for the two components in the two columns, is used to predict peak separation and to aid in the selection of temperature-pulse initiation times.


Subject(s)
Chromatography, Gas/instrumentation , Sensitivity and Specificity , Temperature
20.
Anal Chem ; 77(7): 2078-84, 2005 Apr 01.
Article in English | MEDLINE | ID: mdl-15801741

ABSTRACT

A series-coupled ensemble of microfabricated GC columns made by dry reactive ion etching of silicon substrates is evaluated for use with pneumatic selectivity enhancement techniques for targeted pairs of volatile organic compounds. Each column is 3.0 m long with a 150 miceom wide by 240 microm deep cross section. Dynamic coating was used to prepare a nonpolar column with a dimethyl polysiloxane stationary phase and a moderately polar column with a trifluoropropylmethyl polysiloxane stationary phase. Each column generates 5000-6000 theoretical plates. The columns are operated in series with the nonpolar column connected to a split inlet, the polar column connected to a flame ionization detector, and a valve connected between the column junction point and the inlet to the first column. When the valve is closed, the effluent from the first column passes directly into the second column. When the valve is open, both ends of the first column are at the inlet pressure, and flow stops in this column while increased flow is obtained in the second column. For analyte pairs that are separated by the first column but coelute from the column ensemble, the valve is opened for a few seconds after the first component of the pair has passed into the second column but the second component is still in the first column. The result is enhanced separation of the pair in the ensemble chromatogram. Relatively thick cross-linked stationary-phase films are used to increase retention for volatile compounds. The combination of air carrier gas and stationary-phase film thickness in the range 1-2 microm requires the use of relatively low average carrier gas velocities (typically less than 10 cm/s) for adequate resolving power of the column ensemble. Selectivity enhancement under isothermal conditions for a 14-component mixture of volatile organic compounds is demonstrated where neither of the columns alone nor the column ensemble without selectivity enhancement could obtain a complete separation.


Subject(s)
Chromatography, Gas/instrumentation , Chromatography, Gas/methods , Air , Equipment Design , Silicon
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