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Articles Complete Mass Spectrometry/Mass Spectrometry Data Field Acquisition on the Chromatographic Time Scale by TimeResolved Ion Momentum Spectrometry with Time-Array Detection 1362 Measurement of ion flight times by using time array detec tion in a magnetic sector mass spectrometer allows for a complete MS/MS fragmentation data field to be collected as the compound emerges during a single 10-s chromatographic peak. B. A. Eckenrode, J. T. Watson, and C. G. Enke*, Department of Chemistry, Michigan State University, East Lansing, MI 48824 and J. F. Holland, Department of Biochemistry, Michigan State Uni versity, East Lansing, MI 48824 Determination of Trace Elements in Zirconium Samples by a Gas-Jet-Enhanced Sputtering Source Mass Spectrometer 1368 The analysis of a zirconium alloy is studied by using a gasjet-enhanced sputtering source mass spectrometer. Interfer ences are reduced and detection limits are generally im proved. Hyo J. Kim and Edward H. Piepmeier*, Department of Chemis try, Oregon State University, Corvallis, OR 97331 and Gary L. Beck, Gary G. Brumbaugh, and O. Thomas Farmer, III, Analyt ical Laboratory, Teledyne Wah Chang Albany, Albany, OR 97321 Screening of Solid Commercial Pharmaceuticals Using Ion Mobility Spectrometry 1374 A hand-held ion mobility spectrometer and IMS/MS are used to characterize the active ingredients in analgesic medi cines. Mobility spectra of over-the-counter formulations are obtained by screening vapors above warmed powders. Gary A. Eiceman*, Department of Chemistry, New Mexico State University, Las Cruces, NM 88003-0003, David A. Blyth, GeoCenters, Inc., Ft. Washington, MD 20744, and Donald B. Shoff and A. Peter Snyder, SMCCR-RSL, U.S. Army Chemical Research, Development and Engineering Center, Aberdeen Proving Ground, MD 21010-5423 Simultaneous Deactivation and Coating of Porous Silica Particles for Microcolumn Supercritical Fluid Chromatography 1379 Poly(octyl- and poly(octadecylhydrosiloxane) polymers are bonded directly to porous silica packing materials, produc ing a less active surface than conventional bonded-phase packings. Kent M. Payne, Bryon J. Tarbet, Jerald S. Bradshaw, Karin E. Markides, and Milton L. Lee*, Department of Chemistry, Brigham Young University, Provo, UT 84602 * Corresponding author 756 A · ANALYTICAL CHEMISTRY, VOL. 62, NO. 14, JULY 15, 1990

Multidimensional Packed Capillary Coupled to Open Tubular Column Supercritical Fluid Chromatography Using a ValveSwitching Interface 1384 An on-line 2D supercritical fluid chromatograph with a rota ry valve interface and cryofocusing is constructed. Grouptype separation in the first dimension, followed by shapeselective separation in the second dimension, is used to illus trate fast separations and trace-level enrichment. Z. Juvancz, Κ. M. Payne, Κ. Ε. Markides, and M. L. Lee*, De partment of Chemistry, Brigham Young University, Provo, UT 84602 Chlorodifluoromethane as the Mobile Phase in Supercritical Fluid Chromatography of Selected Phenols 1389 The usefulness of chlorodifluoromethane as an alternative supercritical fluid to CO2 for the determination of polar solutes is studied. A standard mixture of five phenols is analyzed using a capillary column with UV detection at 280 nm. Chye Peng Ong, Hian Kee Lee, and Sam Fong Yau Li*, Depart ment of Chemistry, National University of Singapore, Kent Ridge, Republic of Singapore 0511 Solute Focusing in Flow Injection Analysis: Limits of Detection and Linear Dynamic Range 1392 On-line solute focusing gives limits of detection independent of injection volume and reduced peak broadening (compared with traditional FIA), and eliminates split peaks in on-line reaction analyses. Beverly F. Johnson and John G. Dorsey*, Department of Chem istry, University of Cincinnati, Cincinnati, OH 45221-0172 Characterization of Formaldehyde and Formaldehyde-Releasing Preservatives by Combined Reversed-Phase Cation-Exchange High-Performance Liquid Chromatography with Postcolumn Derivatization Using Nash's Reagent 1397 Formaldehyde and three formaldehyde-releasing preserva tives are resolved in a single chromatogram. The LOD is ~400 ppb, RSD is 0.5%, and the linear dynamic range spans two decades. William Russell Summers, Buckman Laboratories International, Inc., P.O. Box 8305, Memphis, TN 38108-0305 Water in Oil Microemulsions as Mobile Phase in Liquid Chromatography

1402

The water content of a water-heptane-Aerosol OT microemulsion, used as a mobile phase in a silica column, induces drastic changes in test solute retention and selectivity, col umn permeability, column dead volume, and surfactant ad sorption. Alain Berthod*, Odile Nicolas, and Maurice Porthault, Labora toire des Sciences Analytiques, UA CNRS 435, Université de Lyon 1, 69622 Villeurbanne cedex, France

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Ion Binding by Poly{pyrrole-co-[3-(pyrrol-1-yl)propanesulfonate]} Thin Films

1407

The ion binding property of the biconductive polymer is demonstrated and quantitated using cyclic voltammetry along with UV-vis spectrophotometry. Inorganic complexes bearing multiple positive charges, namely Ru(NH3)6 3+ and Ru(bpy)3 2+ (bpy = 2,2'-bipyridyl), are used as model ions. Sanjay Basak and Krishnan Rajeshwar*, Department of Chemistry, The University of Texas at Arlington, Arlington, TX 760190065 and Masao Kaneko, Institute of Physical and Chemical Research, Wako, Saitama 351-01, Japan Catalytic Oxidation and Flow Detection of Carbohydrates at Ruthenium Dioxide Modified Electrodes 1413 Ruthenium dioxide modified carbon paste electrodes offer a marked decrease in overpotentials for the oxidation of carbohydrate compounds. The electrocatalytic behavior is exploited for sensitive and stable, fixed-potential, amperometric monitoring of carbohydrates in flowing streams. Joseph Wang* and Ziad Taha, Department of Chemistry, New Mexico State University, Las Cruces, NM 88003 Solvent Modulation in Liquid Chromatography: General Concept and Theory 1416 In solvent modulation, individual solvent zones are introduced onto the chromatographic column in a random or repeating sequence. Based on theoretical predictions, the solvent delivery method provides a versatile and accurate means of controlling and predicting solute retention in LC. Jon H. Wahl, Christie G. Enke, and Victoria L. McGuffin*, Department of Chemistry, Michigan State University, East Lansing, MI 48824 Determination of Trace Amounts of Vanadium in Natural Waters and Coal Fly Ash with 2-(8-Quinolylazo)-5-(dimethylamino)phenol by Reversed-Phase Liquid Chromatography-Spectrophotometry 1424 The detection limit for the reversed-phase liquid chromatographic determination of vanadium(V) chelated with 2-(8quinolylazo)-5-(dimethylamino)phenol is 2.6 pg. Many cations including iron(III) and aluminum(IH) do not interfere, allowing for the measurement of vanadium in natural waters and coal fly ash without preseparation or preconcentration. Jun'ichiro Miura, Department of Applied Chemistry and Biotechnology, Fukui University, Bunkyo-3, Fukui, 910 Japan Ion-Selective Electrodes Using an Ionophore Covalently Attached to Carboxylated Poly(vinyl chloride)

1428

A potassium-selective electrode based on benzo-15-crown-5 covalently attached to carboxylated poly(vinyl chloride) is reported. Leaching of the ionophore from the polymer membrane is reduced, as evidenced by the increased lifetime of the electrode. Sylvia Daunert and Leonidas G. Bâchas*, Department of Chemistry and Center of Membrane Sciences, University of Kentucky, Lexington, KY 40506-0055

758 A · ANALYTICAL CHEMISTRY, VOL. 62, NO. 14, JULY 15, 1990

Synthetic Chemoreceptive Membranes. Sensing Bitter or Odorous Substances on a Synthetic Lipid Multibilayer Film by Using Quartz-Crystal Microbalances and Electric Responses 1431 Specific adsorption and detection of bitter and odorous substances on a synthetic lipid membrane can be determined by observing frequency changes of a lipid-coated quartz-crystal microbalance and changes of membrane potential and resistance. Yoshio Okahata*, Gen-ichiro En-na, and Hiroshi Ebato, Department of Polymer Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152, Japan Surface-Enhanced Resonance Raman Spectroscopy of Liquid Chromatographic Analytes on Thin-Layer Chromatographic Plates 1438 Liquid chromatographic effluents are deposited onto a TLC plate followed by the addition of Ag sol. A limit of detection of 750 fmol is obtained for pararosaniline acetate. The postaddition of Ag sol prevents continued aggregation and allows for time-independent Raman analysis. Steven A. Soper, Kenneth L. Ratzlaff, and Theodore Kuwana*, The Center for Bioanalytical Research and the Department of Chemistry, The University of Kansas, Lawrence, KS 66046 Nondestructive Analytical Procedure for Simultaneous Estimation of the Major Classes of Hydrocarbon Constituents of Finished Gasolines 1444 Near-IR spectroscopy in both the short- (700-1200 nm) and long-wavelength (1100-2500 nm) regions is used to simultaneously estimate aliphatic, aromatic, and olefinic compounds in finished gasolines. The test requires 1-3 mL of gasoline. Jeffrey J. Kelly and James B. Callis*, Center for Process Analytical Chemistry, Department of Chemistry, BG-10, University of Washington, Seattle, WA 98195 Determination of Subnanogram per Cubic Meter Concentrations of Metals in the Air of a Trace Metal Clean Room by Impaction Graphite Furnace Atomic Absorption and Laser Excited Atomic Fluorescence Spectrometry 1452 Reproducibility of two sets of measurements made seven months apart is 23% and short-term reproducibility is 1 3 34%, depending on concentration. Fluorescence improved lead detection limits over absorption by 2 orders of magnitude. Zhongwen Liang, Guor-Tzo Wei, Richard L. Irwin, Andrew P. Walton, and Robert G. Michel*, Department of Chemistry, University of Connecticut, 215 Glenbrook Road, Storrs, CT 06269-3060 and Joseph Sneddon, Department of Chemistry, University of Lowell, 1 University Avenue, Lowell, MA 01854

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Determination of Physiological Levels of Glucose in an Aqueous Matrix with Digitally Filtered Fourier Transform Near-Infrared Spectra 1457

Determination of Chloroaniline Traces in Environmental Waters by Selective Extraction with Two Traps in Tandem and Liquid Chromatography 1490

Digital filtering techniques are designed to determine glu cose from the background absorbance of water in Fourier transform near-IR spectra. By combining numerical optimi zation techniques with Fourier filtering, a calibration strate gy is devised that allows glucose to be quantitated in the 120-mM range. Mark A. Arnold and Gary W. Small*, Department of Chemistry, The University of Iowa, Iowa City, IA 52242

Selective liquid-solid extraction is achieved by using a trap containing a nonspecific adsorbing material in tandem with another trap containing a resin-based strong cation ex changer. Recoveries are better than 88%, and the detection limits are below 0.1 μgίL·. Antonio Di Corcia* and Roberto Samperi, Dipartimento di Chimica, Université La Sapienza di Roma, Piazzale Aldo Moro 5,00185 Roma, Italy

Direct Analysis of Bacterial Fatty Acids by Curie-Point Pyrolysis Tandem Mass Spectrometry

Automated High-Performance Liquid Chromatography for the Determination of Pesticides in Water Using Solid Phase Extraction 1495

1465

Fatty-acid-derived mass spectral peaks are identified in py rolysis mass spectra of five bacterial species and are used for differentiating the organisms. Stephan DeLuca, Emory W. Server, Peter de B. Harrington, and Kent J. Voorhees*, Colorado School of Mines, Golden, CO 80401 Derivatization of Benz[a]anthracene Metabolites for Detection by Laser Excited Shpol'skii Spectrometry 1472 Shpol'skii spectra of polar polycyclic aromatic compounds are achieved by using a derivatization procedure. Ultra trace level, isomer-selective detection of benz[a]anthracene me tabolites from urine and blood sera matrices is accom plished. Stephan Weeks, Steven Gilles, Roy Dobson, Scott Senne, and Arthur P. D'Silva*, Ames Laboratory—USDOE, Iowa State Uni versity, Ames, IA 50011 Determination of Gold at Femtomolar Levels in Natural Waters by Flow Injection Inductively Coupled Plasma Quadrupole Mass Spectrometry 1477 Four to eight liters of seawater are preconcentrated to 1 mL by anion exchange of Au as [Au(CN)2~] using 195Au to moni tor recoveries followed by flow injection inductively coupled plasma quadrupole mass spectrometric detection. A 10-fM detection limit and 15% relative precision at the 100-fM level are obtained. Kelly Kenison Falkner* and John M. Edmond, Department of Earth, Atmospheric and Planetary Sciences, E34-246, Massachu setts Institute of Technology, Cambridge, MA 02139 Enhancement of Flow Injection Optosensing by Sorbent Extraction and Reaction Rate Measurement

Pesticides in water are determined at the pptr level. Recoveries range from 84% ± 1.2% to 93% ± 1.0%. Chris H. Marvin and Ian D. Brindle, Department of Chemistry, Brock University, St. Catharines, Ontario L2S 3A1, Canada, C. David Hall, Ontario Ministry of the Environment, Rexdale, Ontario M9W 5L1, Canada, and Mikio Chiba*, Research Station, Agriculture Canada, Vineland Station, Ontario LOR 2E0, Canada Microhole Array Electrode as a Glucose Sensor

1498

Glucose oxidase is immobilized on the surface of a platinized microhole array electrode. The linearity of the electrode current response against glucose concentration and the stability of the electrode are extended by increasing the hole depth. Yoshihiro Shimizu* and Ken-ichi Morita, Basic Research Laboratories, Toray Industries, Inc., 1111 Tebiro, Kamakura 248, Japan Spectroelectrochemical Measurement of Gaseous Oxygen 1502 A gaseous oxygen sensing system uses the spectrophotometric record from the oxidation of a reduced compound continuously regenerated by electrochemistry. The sensor measures partial pressures from a few ppm to 1 atm and can be used to determine polymer permeabilities. Jean Cantet, Philippe Labrune, Alain Bergel, and Maurice Comtat*, Laboratoire de Génie Chimique, URA CNRS 192, Laboratoire de Chimie Physique et Electrochimie, Université Paul Sabatier, 118, route de Narbonne, 31062 Toulouse, France Polymeric Membrane Anion-Selective Electrodes Based on Diquaternary Ammonium Salts 1506

1482

A C-18 packed detector is used in an optosensing mode to preconcentrate and monitor, in real time and simultaneous ly, the reduction of the phosphomolybdate and silicomolybdate heteropoly complexes. The FIA profiles are evaluated using partial least-squares analysis with cross validation, providing a differential kinetics model for determining both components. Nathan Lacy, Gary D. Christian*, and Jaromir Ruzicka*, De partment of Chemistry, BG-10, University of Washington, Seattle, WA 98195


The influence of the ionophore structure on the anion selectivity of membrane electrodes based on diquaternary ammonium salts is reported. Selectivity for iodide is achieved with a detection limit of 4.2 Χ 10" 7 M. Vanessa J. Wotring, David M. Johnson, and Leonidas G. Bâchas*, Department of Chemistry and Center of Membrane Sciences, University of Kentucky, Lexington, KY 40506-0055

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Polymeric Membrane Sodium-Selective Electrodes Based on Lipophilic Calix[4]arene Derivatives 1510

Technical Notes

Sodium ion-selective polymeric membrane electrodes based on lipophilic calix[4]aryl ester and amide derivatives are fabricated. T h e s e electrodes are highly ion selective and can be used for sodium assays of human sera. Keiichi Kimura*. Tsutomu Miura, Mitsunori Matsuo, and Toshiyuki Shono, Department of Applied Chemistry, Faculty of Engineering, Osaka University, Yamada-oka, Suita, Osaka 565, Japan

Liquid Secondary Ion Mass Spectrometry Analysis of Natural and Recombinant Proteins and Monoclonal Antibody Light Chains with Molecular Weights between 16 000 and 25 000 1536 Marshall M. Siegel*, Rushung Tsao, Vivian W. Doelling, and Irwin J. Hollander, American Cyanamid Company, Medical Research Division, Lederle Laboratories, Pearl River, NY 10965

Network Analysis Method Applied to Liquid-Phase Acoustic Wave Sensors 1514

Linearity Considerations for a Near-Infrared Laser Diode Intracavity Absorption Spectrophotometer 1543

T h e bulk acoustic wave quartz sensor in liquid is completely characterized by the network analysis method. T h e results disprove the validity of t h e modified Sauerbrey theory. Arlin L. Kipling and Michael Thompson*, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada M5S 1A1

James Hicks and Gabor Patonay*, Georgia State University, Department of Chemistry, Atlanta, GA 30303

Device for Subambient Temperature Control in Liquid Chromatography

High-Performance Liquid Chromatography/Chemical Ionization Mass Spectrometry Analysis of Pyrolysates of Amylose and Cellulose 1519

Effects of Ion Source Parameters on Ion Beam Energy in Mass Spectrometry 1547

Anhydrooligosaccharides and related compounds with attached ring-cleavage fragments are isolated as perbenzoylated derivatives from Curie-point pyrolysates. These compounds are confirmed to be real pyrolysis products and not M S artifacts. Peter W. Arisz*, James A. Lomax, and Jaap J. Boon, Unit for Mass Spectrometry of Macromolecular Systems, FOM-Institute for Atomic and Molecular Physics, Kruislaan 407,1098 SJ Amsterdam, The Netherlands

Kuangnan Qian, Anil Shukla*, and Jean Futrell, Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716

Direct Control of the Electroosmosis in Capillary Zone Electrophoresis by Using an External Electric Field

1523

David K. Ryan* and Lisa S. Ventry, Edgerton Research Laboratory, New England Aquarium, Boston, MA 02110, Stephen E. Cabaniss*, Department of Chemistry, Kent State University, Kent, OH 44242, and Mark S. Shuman, Department of Environmental Science and Engineering, University of North Carolina, Chapel Hill, NC 27599-7400

Correction. Nile Red as a Solvatochremic Dye for Measuring Solvent Strength in Normal Liquids and Mixtures of Normal Liquids with Supercritical and Near Critical Fluids 1552 Jerry F. Deye and T. A. Berger*, Hewlett-Packard, P.O. Box 900, Route 41 and Starr Road, Avondale, PA 19311-0900 and Albert G. Anderson, Central Research and Development Department, E. I. du Pont de Nemours and Co., Wilmington, DE 19880-0328

Fiber-Optic Potassium Ion Sensor Using Alkyl-Acridine Orange in Plasticized Poly(vinyl chloride) Membrane 1528 Yuji Kawabata, Ryuichi Tahara, Toshito Kamichika, Totaro Imasaka, and Nobuhiko Ishibashi*, Faculty of Engineering, Kyushu University, Hakozaki, Fukuoka 812, Japan

Multiway Analysis of Variance for the Interpretation of Interlaboratory Studies

1550

Cheng S. Lee*, William C. Blanchard, and Chin-Tiao Wu, Department of Chemical and Biochemical Engineering, University of Maryland Baltimore County Campus, Baltimore, MD 21228, and Blanchard & Co., Inc., 27 Glen Alpine Road, Phoenix, MD 211312407

Correspondence Exchange of Comments on Fluorescence Quenching Measurements of Copper-Fulvic Acid Binding

1545

Lane C. Sander* and Neal E. Craft, National Institute of Standards and Technology, Center for Analytical Chemistry, Gaithersburg, MD 20899

1531

Neil E. Jones, Michigan Department of Agriculture, Laboratory Division, East Lansing, MI 48823

Background Emission from the Peroxyoxalate Chemiluminescence Reaction in the Absence of Fluorophors 1532 B. Mann and M. L. Grayeski", Department of Chemistry, Seton Hall University, South Orange, NJ 07079


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