briefs - ACS Publications - American Chemical Society

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BRIEFS Perspective: Analytical Biotechnology DNA Amplification by the Polymerase Chain Reaction

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PCR involves the enzymatic amplification of nucleic acid sequences via repeated cycles of denaturation, oligonucleotide annealing, and DNA polymerase extension. The history, principles, and practical considerations are described. Richard A. Gibbs, Institute for Molecular Genetics, Baylor College of Medicine, One Baylor Plaza, Houston, TX 77030

Articles Development of a Statistical Model for Metal-Humic Interactions

Studies of Chemical Interferences in an Inductively Coupled Plasma Using Moment Analysis of Space-Resolved Emission Profiles 1233 Interelement effects of sodium, aluminum, and phosphate ion on calcium and magnesium emissions in an inductively coupled plasma are characterized by rate constant variations. K. P. Li, Department of Chemistry, University of Lowell, Lowell, MA 01854 and J. D. Hwang and J. D. Winefordner*, Department of Chemistry, University of Florida, Gainesville, FL 32611 Inductively Coupled Plasma Axial Viewing Absorption Technique

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Proton and metal-humic interactions in a three-cation system consisting of any metal ion of interest are characterized by lanthanide ion probe spectroscopy using a Eu 3 + probe in aqueous media and a statistical model. W. Susetyo, J. C. Dobbs, and L. A. Carreira*, Dept. of Chemistry, University of Georgia, Athens, GA 30602 and L. V. Azarraga and D. M. Grimm, Environmental Research Laboratory, EPA, Athens, GA 30613 Use of a Surface-Acoustic-Wave Sensor To Characterize the Reaction of Styrene Vapor with a Square-Planar Organoplatinum Complex 1222 The olefin substitution reaction between styrene vapor and the solid square-planar jr-complex trans-PtC^iethylene) (pyridine) is examined using a SAW sensor. The sensor response is proportional to the rate of the heterogenous reaction and can be related to the styrene concentration. Edward T. Zellers*, Richard M. White, and Stephen M. Rappaport, Dept. of Environmental and Industrial Health, School of Public Health, University of Michigan, Ann Arbor, MI 48109-2029, Dept. of Electrical Engineering and Computer Sciences and Berkeley Sensor and Actuator Center, University of California, Berkeley, CA 94720, and Dept. of Biomedical and Environmental Health Sciences, School of Public Health, University of California, Berkeley, CA 94720 Selective Real-Time Measurement of Styrene Vapor Using a Surface-Acoustic-Wave Sensor with a Régénérante Organoplatinum Coating 1227 Selective measurement of styrene vapor in the presence of several olefin and nonolefin interferences is achieved by using a SAW sensor coated with a mixture of transPtCl2(ethylene)(pyridine) and poly(isobutylene). Edward T. Zellers*, Noralynn Hassold, Richard M. White, and Stephen M. Rappaport, Department of Environmental and Industrial Health, School of Public Health, University of Michigan, Ann Arbor, MI 48109-2029, Department of Electrical Engineering and Computer Sciences and Berkeley Sensor and Actuator Center, University of California, Berkeley, CA 94720, and Department of Biomedical and Environmental Health Sciences, School of Public Health, University of California, Berkeley, CA 94720 * Corresponding author 690 A • ANALYTICAL CHEMISTRY, VOL. 62, NO. 13, JULY 1, 1990

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An atomic absorption technique involving axial viewing of an inductively coupled argon plasma is developed. The technique is used to determine Ag, Cu, and Mg. Gary D. Rayson* and Daniel Y. Shen, Chemistry Department, New Mexico State University, Box 30001, Las Cruces, NM 88003 Photocatalytic Chemiluminescence Detection of Quinones in High-Performance Liquid Chromatography 1242 A catalytic, postcolumn photochemical reaction scheme coupled with peroxyoxalate chemiluminescence provides sensitive (subpicomole range) and selective detection of anthraquinone and naphthoquinone derivatives. James R. Poulsen and John W. Birks*, Department of Chemistry and Biochemistry and Cooperative Institute for Research in Environmental Sciences (CIRES), Campus Box 216, University of Colorado, Boulder, CO 80309 Voltammetric Anion Responsive Sensors Based on Modulation of Ion Permeability through Langmuir-Blodgett Films Containing Synthetic Anion Receptors 1252 Lipophilic derivatives of macrocyclic polyamine and cyclodextrin polyamine are employed as anion sensors with selectivity and signal amplification based on the voltammetric detection of an analyte-induced modulation of the permeability for marker ion. Shinobu Nagase, Masamitsu Kataoka, Ryuichi Naganawa, Ryoko Komatsu, Kazunori Odashima, and Yoshio Umezawa*, Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060, Japan Off-Lino Coupling of a Microbore High-Performance Liquid Chromatograph to a Secondary Ion Time-of-Flight Mass Spectrometer 1259 The eluent from a microbore HPLC column is electrosprayed from a needle tip. The charged plume is focused by a shaped electrostatic field and hydrodynamic focusing, and then deposited as a dry solid on a substrate surface in a series of circular deposits ~ 1 mm in diameter. R. C. Beavis*, W. Ens, D. E. Main, and K. G. Standing, Department of Physics, University of Manitoba, Winnipeg, Manitoba, Canada R3T 2N2

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Membrane Mass Spectrometry for the Direct Trace Analysis of Volatile Organic Compounds in Air and Water 1265 Membrane sampling of organic compounds in water and air is most efficient with thin membranes, at low temperatures, and with mixing at the sample/membrane interface. Sam­ pling efficiency is also dependent on membrane inlet config­ uration. Mark A. LaPack*, James C. Tou, and Christie G. Enke, Analyti­ cal Sciences Laboratory, The Dow Chemical Company, Midland, MI 48667, and Department of Chemistry, Michigan State Universi­ ty, East Lansing, MI 48824 Mass Spectrometry of Technetium at the Subprogram Level 1271 Blue M has a bath to meet your needs. Water, Oil, Refrigerated models including Shaker, Hydrometer and Full Visibility Jar designs from 0 C to + 260 C. Most feature the patented Magni-Whirl® agitation that made conventional circulating systems obso­ lete. Quality-built and available for immediate delivery. Contact your local laboratory distributor or Lindberg/ Blue M, 304 Hart Street, Watertown, WI 53094. Phone 414-261-7000 · FAX 414-261-0925. 1089 A

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Time-of-flight secondary ion mass spectra are obtained from thin films of perfluorinated poly- and copolyethers up to m/z 6500. Fragmentation patterns are unique and reproducible for each kind of poly- and copolyether, independent of sam­ ple preparation and substrate. loannis V. Bletsos and David M. Hercules*, Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, David Fowler, IBM Research Division, San Jose, CA 95120, and Dieter vanLeyen and Alfred Benninghoven, Physikalisches Institut, Universitât Munster, D-4400 Munster, Federal Republic of Germany Electrospray Ionization Combined with Ion Trap Mass Spectrometry

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Surface-Induced Dissociation by Fourier Transform Mass Spectrometry 1295 A detailed procedure for performing surface-induced dissociation of both electron ionization and laser-desorbed ions in a dual-cell Fourier transform mass spectrometer is described. Carl F. Ijames and Charles L. Wilkins*, Department of Chemistry, University of California, Riverside, CA 92521

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Time-of-Flight Secondary Ion Mass Spectrometry of Perfluorinated Polyethers

Ions formed via electrospray are injected into and analyzed with a quadrupole ion trap mass spectrometer. Data are shown for multiply charged anions and cations. Gary J. Van Berkel, Gary L. Glish, and Scott A. McLuckey*, Analytical Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6365

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A method for the determination of >10 6 atoms of 98 Tc or 97 Tc and 5 Χ 106 atoms of " T c by negative thermal ioniza­ tion MS is described. Donald J. Bokop*, Norman C. Schroeder, and Kurt Wolfsberg, Isotope and Nuclear Chemistry Division, Los Alamos National Lab­ oratory, Los Alamos, NM 87545

Capillary Supercritical Fluid Chromatography at Pressures above 400 atm 1299 v^rvl

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692 A • ANALYTICAL CHEMISTRY, VOL. 62, NO. 13, JULY 1, 1990

Systems limited to ~400 atm are not able to access densities needed for many applications, especially when temperatures are raised to adjust selectivity. A modest improvement to 560 atm is beneficial, but much higher pressures are still needed. T. L. Chester*, D. J. Bowling, D. P. Innis, and J. D. Pinkston, The Procter & Gamble Company, Miami Valley Laboratories, P.O. Box 398707, Cincinnati, OH 45239-8707

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BRIEFS Optimization of Micellar Electrokinetic Chromatography 1302 A theory for the optimization of resolution and resolution per unit time is evaluated. Equations are derived to predict the optimum retention factor and the corresponding surfac­ tant concentration to use. Joe P. Foley, Department of Chemistry, Louisiana State Universi­ ty, Baton Rouge, LA 70803-1804 Indirect Stereoselective Determination of the Enantiomers of a Thieno[2,3-6]thiopyran-2-sulfonamide in Biological Fluids 1308 A sensitive (12.5 ng/mL) assay for the determination of stereoisomers of a thieno[2,3-6]thiopyran-2-sulfonamide and its hydroxy metabolite in biological fluids is developed. The disposition of the enantiomers in humans is highly stereoselective. No interconversion of the isomers is ob­ served in vivo. B. K. Matuszewski*, M. L. Constanzer, G. A. Hessey II, and W. F. Bayne, Merck Sharp & Dohme Research Laboratories, West Point, PA 19486 Thermodynamic Properties in Micellar Liquid Chromatography Based on the Three-Phase Equilibrium Model 1315 The retention mechanism of micellar chromatography is described in terms of equilibrium and thermodynamic prop­ erties. The change in enthalpy for the two principal equilib­ ria is obtained. Frank P. Tomasella and L. J. Cline Love*, Department of Chem­ istry, Seton Hall University, South Orange, NJ 07079 Liquid Chromatography/Time-of-Flight Mass Spectrometry with High-Speed Integrated Transient Recording 1319 Combined HPLC/MS experiments are carried out on a timeof-flight mass spectrometer using a continuous-flow probe and a high-speed integrated transient recording system. W. Bart Emary, Ihor Lys, and Robert J. Cotter*, Department of Pharmacology and Molecular Sciences, The Johns Hopkins Univer­ sity, Baltimore, MD 21205, Richard Simpson, Department of Chemistry, University of Maryland Baltimore County, Baltimore, MD 21228, and Andrew Hoffman, Kratos Analytical, Manchester M31 2LD, England

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Square-Wave Anodic Stripping Voltammetry at Glassy-CarbonBased Thin Mercury Film Electrodes in Solutions Containing Dissolved Oxygen 1325 Trace lead and cadmium in solutions containing oxygen are determined using square-wave anodic stripping voltam­ metry at conventional-size thin mercury film electrodes. Similar determinations by differential pulse anodic strip­ ping voltammetry are not possible unless oxygen is removed from the solution. Marek Wojciechowski* and John Balcerzak, Department of Chemistry and Biochemistry, University of Maryland, Baltimore County Campus, Baltimore, MD 21228

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694 A • ANALYTICAL CHEMISTRY, VOL. 62, NO. 13, JULY 1, 1990

BRIEFS

The Journal of Organic Chemistry

solicits manuscripts that address topics at the interface of organic chemistry and biology.

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hile such manuscripts should address fundamental problems in organic chemistry (structure, mechanism, synthesis), we encourage submission of manuscripts in which these problems are solved with the use of techniques not traditionally associated with organic chemistry (enzyme kinetics, enzyme isolation and purification, identification of active site residues, etc.). The Journal hopes to foster integrated publications in which the chemical aspects are not separated from the biological aspects. For manuscript format, see J. Org Chem, 1990, 55 (1), 7A-10A. Send manuscripts to: C H. Heathcock, Editor-in-Chief; The Journal of Organic Chemistry. Department of Chemistry: University of California; Berkeley, CA 94720

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696 A • ANALYTICAL CHEMISTRY, VOL. 62, NO. 13, JULY 1, 1990

Computer-Based Instrument for Alternating Current Impedance and High-Frequency Alternating Current Electrochemical Measurements 1331 A digital instrument that measures ac impedance, ac voltammetry, second harmonic ac voltammetry, and squarewave voltammetry is developed. The upper limit of the fre­ quency range is 100 kHz. Peixin He* and Xiaoming Chen, Department of Chemistry, Fudan University, Shanghai 200433, People's Republic of China

Laser Microfabrication and Activation of Graphite and Glassy Carbon Electrodes 1339 Laser pulses impinging on ordered graphite or coated glassy carbon are used to fabricate single microelectrodes or microelectrode arrays with microdisk diameters as small as 2.5 μ,τα. Kent D. Sternitzke and Richard L. McCreery*, Department of Chemistry, The Ohio State University, Columbus, OH 43210

Application of Reversal Electron Attachment for Ultrasensitive Detection of Thermal Electron-Attaching Molecules: CCI4 and C 6 H 5 N0 z 1345 A detection limit below 1.0 pptrv without sample preconcentration or derivatization and without mass spectral interfer­ ences is achieved for CCI4 in N2 using the reversal electron attachment detector. The reversal electron attachment spectrum for C6H5NO2 is also presented. Mark T. Bernius and Ara Chutjian*, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109

Correspondence Direct Characterization of Phthalic Acid Isomers in Mixtures Using Surface-Enhanced Raman Scattering 1349 Job M. Bello, David L. Stokes, and Tuan Vo-Dinh*, Advanced Monitoring Development Group, Health and Safety Research Divi­ sion, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6101

Technical Notes High Precision Arbitrary Waveform Generator for Ion Selection in Fourier Transform Ion Cyclotron Resonance 1352 Curtiss D. Hanson, Mauro E. Castro, Eric L. Kerley, and David H. Russell*, Department of Chemistry, Texas A&M University, College Station, TX 77843

Salting-Out Solvent Extraction for Preconcentration of Neutral Polar Organic Solutes from Water 1355 Daniel C. Leggett*, Thomas F. Jenkins, and Paul H. Miyares, Research Division, U.S. Army Cold Regions Research & Engineer­ ing Laboratory, Hanover, NH 03755

Differential Densometric Analysis of Equilibria in Highly Concentrated Media: Determination of the Aqueous Second Acid Dissociation Constant of H2S 1356 Stuart Licht*, Fardad Forouzan, and Kevin Longo, Department of Chemistry, Clark University, Worcester, MA 01610