Mass Spectrum of D=11 Supergravity on AdS2 x S2 x T7

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orbitrap exploris

orbitrap exploris

orbitrap exploris(中英文实用版)英文文档:The Orbitrap Exploris is a powerful mass spectrometer designed for high-resolution, high-accuracy mass analysis.It utilizes a unique trap-based technology that allows for the separation and detection of ions based on their mass-to-charge ratio (m/z).This instrument is widely used in various fields such as proteomics, metabolomics, environmental analysis, and pharmaceutical research.The Orbitrap Exploris offers several advantages over other mass spectrometry techniques.Firstly, it provides excellent resolution, which enables the identification of complex peaks and the separation of closely related ions.This is particularly useful for the analysis of complex samples, where the presence of numerous interfering peaks can complicate the interpretation of the data.Secondly, the Orbitrap Exploris offers high accuracy in mass measurement, which is crucial for the accurate determination of the molecular weights and structures of unknown compounds.This feature makes it an ideal choice for protein and peptide analysis, as well as for the characterization of small molecules and metabolites.Furthermore, the Orbitrap Exploris is capable of high-throughput analysis, allowing for the rapid screening and characterization of largenumbers of samples.This is particularly beneficial for high-throughput screening applications in the pharmaceutical industry, as well as for large-scale proteomics and metabolomics studies.In summary, the Orbitrap Exploris is a state-of-the-art mass spectrometer that offers high-resolution, high-accuracy mass analysis, making it an invaluable tool for researchers in various fields.中文文档:Orbitrap Exploris 是一款强大的质谱仪,设计用于高分辨率、高准确度的质量分析。

MassSpectrometryIntroduction:质谱法介绍

MassSpectrometryIntroduction:质谱法介绍

©2013 Gregory R. Cook, NDSU
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Time of Flight MS
‣ Ions are accelerated and allowed to drift. Heavier
ions will be accelerated to a lesser velocity than lighter ions.They are separated by the velocities over time. Lighter atoms will impact the detector first.
under the high energy conditions).
‣ The Most Abundant Peak in the Mass Spectrum
is called the BASE PEAK.
©2013 Gregory R. Cook, NDSU
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Thursday, February 7, 13
‣ less fragmentation (and less structural info)
©2013 Gregory R. Cook, NDSU
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EI and CI Comparison
©2013 Gregory R. Cook, NDSU
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Mass Spectrometry Introduction
Chem 744 Spring 2013
©2013 Gregory R. Cook, NDSU Thursday, February 7, 13

InterpretationofMassSpectra:质谱解析

InterpretationofMassSpectra:质谱解析

Interpretation of Mass SpectraBy Fred W. MclaffertyInterpretation of Mass Spectra Details:Mass spectral interpretation for chromatographersMass spectral interpretation for chromatographers This material is designed to helpGC/MS beginners who want to understand a few mass spectral interpretation basics. Interpretation of Mass Spectra Interpretation of Mass Spectra ...INTERPRETATION OF MASS and TANDEM MASS SPECTRA FOR STRUCTURE I. FRAGMENTATION OF GAS-PHASE IONS There are two main classes of fragmentation of radical cations in EIMS:Interpretation of Mass Spectra - Chemistry Courses: About ...Choose a reasonable structure Do the expected fragments agree w/ chosen structure YES NO Interpretation of Mass Spectra Is the structure unique? YESInterpretation of Mass Spectra Interpretation of Mass Spectra ...C. EXAMPLE CID OR PRODUCT-ION SPECTRA Figure 29. Product-ion spectrum of peptide found in proteomics experiment (sequence given in figure). Most of ions are y ions and singly chargedInterpretation of Mass Spectra - United States Home | AgilentCourse Outline Day One • GC-MS Data Structure • Chemistry Review • Data Acquisition Day Two • Introduction to Interpretation Goals • Structural InformationInterpretation of Mass Spectra Part 5 - UCO - BiologyPostulation of Molecular Structures • Put everything together using SIP • There are several major kinds of structural information available from the MSComputer-Assisted Interpretation of Mass SpectraJOHNS HOPKINS APL TECHNICAL DIGEST, VOLUME 20, NUMBER 3 (1999) 363 COMPUTER-ASSISTED INTERPRETATION OF MASS SPECTRA UComputer-Assisted Interpretation of Mass SpectraInterpretation of Mass Spectra Including those from ...Interpretation of Mass Spectra Including those from Electrospray and MALDI Presented by J. Throck Watson Professor, Biochemistry and ChemistryInterpretation of CID Mass SpectraInterpretation of CID Mass Spectra I. API BASICS FOR THE INTERPRETATION OF CID MASS SPECTRA 1. Interpretation Introduction and Isotopes. 2. Masses of Isotopes and Compound MW’S.Advanced Interpretation of Mass Spectra - United States Home ...Course Outline Day One • Performance Verification • QA and QC Measurements • Mass Resolution • Tuning • Review of Fundamental Principles • Element CompositionMass spectra interpretation system including spectra extraction( 1 of 1) United States Patent 5,453,613 Gray , et al. September 26, 1995 Mass spectra interpretation system including spectra extraction AbstractInterpretation of Infrared Spectra, A Practical Approachmass of sulfur, compared with oxygen, results in the characteristic group frequencies occurring at noticeably lower frequencies than the oxygen-containing analogs, ... INTERPRETATION OF INFRARED SPECTRA, A PRACTICAL APPROACH 23 REFERENCES 1.Interpretation of Organic Spectra - Research and Markets4.4.6 Examples of the interpretation of mass spectra from soft ionization 120 4.5 Interpretation of high resolution mass spectra 123 4.6 Interpretation of mass spectra from tandem mass spectrometry 126 References 127 5 Interpretation of infrared spectra 129Basic rules for the interpretation of atmospheric pressure ...step in the interpretation of mass spectra regardless of theioniza-tiontechniqueused.APItechniquesbelongtothegroupofso-called soft ionization techniques, so it is evident already from this name that the ionization process has a softer character in comparison toAutomated Interpretation of Mass Spectra by Incremental ...Rules ? Syntax of the applied fragmentation rules: IF (side1 AND side2) THEN (P(side1) AND P(side2)) where side1 and side2 represent subgraphs of the two possible fragments Interpretation of EI organometallics mass spectra LS in ...60 years of the Faculty of Chemical Technology and Engineering UT & LS in Bydgoszcz 246 • nr 4/2011 • tom 65 Interpretation of EI organometallics mass spectraIntroduction to Mass Spectral InterpretationIntroduction to Mass Spectral Interpretation by Robert Kobelski Each mass spectrum contains a wealth of information. With higher resolution instruments, faster computers, larger and betterOn de novo interpretation of tandem mass spectra for peptide ...On de novo interpretation of tandem mass spectra for peptide identi?cation Vineet Bafna Nathan Edwardsy ABSTRACT The correct interpretation of tandem mass spectra is a di -Mass Spectral Examples - University of AkronMass Spectral Examples We’ve introduced several simple tools to help in the interpretation of mass spectra. Now, lets put them to use and see how wellNovel Bioinformatics Tool: Interpretation of Glycan Mass ...Novel Bioinformatics Tool: Interpretation of Glycan Mass Spectra with Metal Adducts and Multiple Adduct Combinations Julian Saba1, Ningombam Sanjib Meitei 2 and Arun Apte2 Interpretation of Mass Spectral Data 1) The molecular ion1 Interpretation of Mass Spectral Data 1) The molecular ion The molecular ion in an E.I. spectrum may be identified using the following rules: 1) It must be the ion of highest m/z in the spectrum, apart from isotope peaks resulting from its molecularLecture I-1: MS Interpretation-1 - University of Colorado Boulder9 Lecture I-1: MS Interpretation-1 CU- Boulder CHEM 5181 Mass Spectrometry & Chromatography Prof. Jose-Luis Jimenez Fall 2007 Lecture based on an earlier version of notes from Dr. Dan CzizcoInterpretation of Tandem Mass Spectra Obtained from Cyclic ...Interpretation of Tandem Mass Spectra Obtained from Cyclic Nonribosomal PeptidesWei-Ting Liu, †Julio Ng, ‡Dario Meluzzi, Nuno Bandeira, Marcelino Gutierrez,§COMPARISON AND INTERPRETATION OF MASS SPECTRAL DATA OF ...Figure 2: TIC and mass spectrum of 2-bromodiphenyl ether The greater abundance of the doubly charged ion cluster (M-2Br) as compared to the absent orMS basics and spectra interpretationMS Basics What does a mass spectrometer do? A mass spectrometer produces charged particles (ions) from the chemical substances that are to be analyzed.An Introduction to Mass Spectrometry - Widener Universityinterpretation of mass spectra. It is only an introduction and interested readers are encouraged to consult more specialized books and journal articles for additional details. The articles and books referenced in this paper should be available at most college and university libraries.Mass Spectrometry InterpretationInterpretation of Mass Spectra Select a candidate peak for the molecular ion (M+) Examine spectrum for peak clusters of characteristic isotopic patternsIntroduction to Mass SpectroscopyMass Spectrometry: Interpretation of Spectra General Considerations The more stable a fragment (cation or cation radical), the more likely it will be observed in the mass interpretation of mass spectra. Furthermore, such correlations imply that mass spectrometry will provide an important tool for predicting and interpreting photo- chemical reactions. Pith3 and Nicholson4 have shown that the photo- (1) (a) ...Mass Spectrometry: Introduction - University of MinnesotaMass Spectrometry •NOT part of electromagnetic spectrum •What is measured are (typically) positively charged ions •Under certain circumstances negative ionsDownload Interpretation of Mass Spectra Full versionRead This First:We offer two ways that you can get this book for free, You can choose the way you like! You must provide us your shipping information after you complete the survey. All books will be shipped from Amazon US or Amazon UK depending on your region! Please share this free experience to your friends on your social network to prove that we really send free books!Tags:Interpretation of Mass Spectra,Interpretation of Mass Spectra By Fred W. Mclafferty,Interpretation of Mass Spectra PDFDownload Full PDF Version of This Book - FreeDownload Interpretation of Mass Spectra pdf ebooks freeDownload U.S. Nuclear Weapons: Changes In Policy And Force Structure pdf ebooks free Download Digital Photography for Busy Women: How to Manage, Protect and Preserve Your Favorite Photos pdf ebooks freeDownload Die Slowinzen und Lebakaschuben pdf ebooks freeDownload Der jüdische Friedhof in Schwäbisch Hall- Steinbach : Einführung, hebräische Texte mit Übersetzung, Register., Photos: Marion Reuter. Hebräische Übersetzung: Jossi Ben-Arzi und Nathanja Hüttenmeister pdf ebooks freeDownload LEGO® Ninjago #7: Stone Cold pdf ebooks freeDownload Controlling Communicable Disease pdf ebooks freeDownload Practical Aspects of Memory pdf ebooks freeDownload SIGNED Photograph pdf ebooks freeDownload Mischief Again pdf ebooks freeOther PDF Books:John Hull Grundy's Arthropods of Medical Importance pdf ebooks free download by N.R.H. 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标准红外光谱图谱

标准红外光谱图谱

Go to: home • ir • proton nmr • carbon nmr• mass specTable of Contents - IRI. HydrocarbonsII. Halogenated HydrocarbonsIII. Nitrogen Containing CompoundsIV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O And P(=O)-O) VI. Sulfur Containing CompoundsVII. Oxygen Containing Compounds (Except -C(=O)-)VIII. Compounds Containing Carbon To Oxygen Double BondsI. HydrocarbonsA. Saturated Hydrocarbons1. Normal Alkanes2. Branched Alkanes3. Cyclic AlkanesB. Unsaturated Hydrocarbons1. Acyclic Alkenes2. Cyclic Alkenes3. AlkynesC. Aromatic Hydrocarbons1. Monocyclic (Benzenes)2. PolycyclicII. Halogenated HydrocarbonsA. Fluorinated Hydrocarbons1. Aliphatic2. AromaticB. Chlorinated Hydrocarbons1. Aliphatic2. Olefinic3. AromaticC. Brominated Hydrocarbons1. Aliphatic2. Olefinic3. AromaticD. Iodinated Hydrocarbons1. Aliphatic and Olefinic2. AromaticIII. Nitrogen Containing CompoundsA. Amines1. Primarya. Aliphatic and Olefinicb. Aromatic2. Secondarya. Aliphatic and Olefinicb. Aromatic3. Tertiarya. Aliphatic and Olefinicb. AromaticB. PyridinesC. QuinolinesD. Miscellaneous Nitrogen HeteroaromaticsE. HydrazinesF. Amine SaltsG. Oximes (-CH=N-OH)H. Hydrazones (-CH=N-NH2)I. Azines (-CH=N-N=CH-)J. Amidines (-N=CH-N)K. Hydroxamic AcidsL. Azo Compounds (-N=N-)M. Triazenes (-N=N-NH-)N. Isocyanates (-N=C=O)O. Carbodiimides (-N=C=N-)P. Isothiocyanates (-N=C=S)Q. Nitriles (-C≡N)1. Aliphatic2. Olefinic3. AromaticR. Cyanamides (=N-C≡N)S. Thiocyanates (-S-C≡N)T. Nitroso Compounds (-N=O)U. N-Nitroso Compounds (=N-N=O)V. Nitrites (-O-N=O)W. Nitro Compounds (-NO2)1. Aliphatic2. AromaticX. N-Nitro-Compounds (=N-NO2)IV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O and P(=O)-O) VI. Sulfur Containing CompoundsA. Sulfides (R-S-R)1. Aliphatic2. Heterocyclic3. AromaticB. Disulfides (R-S-S-R)C. Thiols1. Aliphatic2. AromaticD. Sulfoxides (R-S(=O)-R)E. Sulfones (R-SO2-R)F. Sulfonyl Halides (R-SO2-X)G. Sulfonic Acids (R-SO2-OH)1. Sulfonic Acid Salts (R-SO2-O-M)2. Sulfonic Acid Esters (R-SO2-O-R)3. Sulfuric Acid Esters (R-O-S(=O)-O-R)H. Thioamides (R-C(=S)-NH2)I. Thioureas (R-NH-C(=S)-NH2)J. Sulfonamides (R-SO2-NH2)K. Sulfamides (R-NH-SO2-NH-R)VII. Oxygen Containing Compounds (Except -C(=O)-)A. Ethers1. Aliphatic Ethers (R-O-R)2. Acetals (R-CH-(-O-R)2)3. Alicyclic Ethers4. Aromatic Ethers5. Furans6. Silicon Ethers (R3-Si-O-R)7. Phosphorus Ethers ((R-O)3-P)8. Peroxides (R-O-O-R)B. Alcohols (R-OH)1. Primarya. Aliphatic and Alicyclicb. Olefinicc. Aromaticd. Heterocyclic2. Secondarya. Aliphatic and Alicyclicb. Olefinicc. Aromatic3. Tertiarya. Aliphaticb. Olefinicc. Aromatic4. Diols5. Carbohydrates6. PhenolsVIII. Compounds Containing Carbon To Oxygen Double BondsA. Ketones (R-C(=O)-R)1. Aliphatic and Alicyclic2. Olefinic3. Aromatic4. α-Diketones and β-DiketonesB. Aldehydes (R-C(=O)-H)C. Acid Halides (R-C(=O)-X)D. Anhydrides (R-C(=O)-O-C(=O)-R)E. Amides1. Primary (R-C(=O)-NH2)2. Secondary (R-C(=O)-NH-R)3. Tertiary (R-C(=O)-N-R2)F. Imides (R-C(=O)-NH-C(=O)-R)G. Hydrazides (R-C(=O)-NH-NH2)H. Ureas (R-NH-C(=O)-NH2)I. Hydantoins, Uracils, BarbituratesJ. Carboxylic Acids (R-C(=O)-OH)1. Aliphatic and Alicyclic2. Olefinic3. Aromatic4. Amino Acids5. Salts of Carboxylic AcidsK. Esters1. Aliphatic Esters of Aliphatic Acids2. Olefinic Esters of Aliphatic Acids3. Aliphatic Esters of Olefinic Acids4. Aromatic Esters of Aliphatic Acids5. Esters of Aromatic Acids6. Cyclic Esters (Lactones)7. Chloroformates8. Esters of Thio-Acids9. Carbamates10. Esters of Phosphorus AcidsPublished by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Go to: home • ir • proton nmr • carbon nmr• mass specTable of Contents - Proton NMRI. HydrocarbonsII. Halogenated HydrocarbonsIII. Nitrogen Containing CompoundsIV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O and P(=O)-O) VI. Sulfur Containing CompoundsVII. Oxygen Containing Compounds (Except -C(=O)-)VIII. Compounds Containing Carbon To Oxygen Double BondsI. HydrocarbonsA. Saturated Hydrocarbons1. Normal Alkanes2. Branched Alkanes3. Cyclic AlkanesB. Unsaturated Hydrocarbons1. Acyclic Alkenes2. Cyclic Alkenes3. AlkynesC. Aromatic Hydrocarbons1. Monocyclic (Benzenes)2. PolycyclicII. Halogenated HydrocarbonsA. Fluorinated Hydrocarbons1. Aliphatic2. AromaticB. Chlorinated Hydrocarbons1. Aliphatic2. AromaticC. Brominated Hydrocarbons1. Aliphatic2. AromaticD. Iodinated Hydrocarbons1. Aliphatic2. AromaticIII. Nitrogen Containing CompoundsA. Amines1. Primarya. Aliphaticb. Aromatic2. Secondarya. Aliphaticb. Aromatic3. Tertiarya. Aliphaticb. AromaticB. PyridinesC. Quaternary Ammonium SaltsD. HydrazinesE. Amine SaltsF. Ylidene Compounds (-CH=N-)G. Oximes (-CH=N-OH)H. Hydrazones (-CH=N-NH2)I. Azines (-CH=N-N=CH-)J. Amidines (-N=CH-N)K. Hydroxamic AcidsL. Azo Compounds (-N=N-)M. Isocyanates (-N=C=O)N. Carbodiimides (-N=C=N-)O. Isothiocyanates (-N=C=S)P. Nitriles (-C≡N)1. Aliphatic2. Olefinic3. AromaticQ. Cyanamides (=N-C≡N)R. Isocyanides (-N≡C )S. Thiocyanates (-S-C≡N)T. Nitroso Compounds (-N=O)U. N-Nitroso Compounds (=N-N=O)V. Nitrates (-O-NO2)W. Nitrites (-O-N=O)X. Nitro Compounds (-NO2)1. Aliphatic2. AromaticY. N-Nitro-Compounds (=N-NO2)IV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O and P(=O)-O) VI. Sulfur Containing CompoundsA. Sulfides (R-S-R)1. Aliphatic2. AromaticB. Disulfides (R-S-S-R)C. Thiols1. Aliphatic2. AromaticD. Sulfoxides (R-S(=O)-R)E. Sulfones (R-SO2-R)F. Sulfonyl Halides (R-SO2-X)G. Sulfonic Acids (R-SO2-OH)1. Sulfonic Acid Salts (R-SO2-O-M)2. Sulfonic Acid Esters (R-SO2-O-R)3. Sulfuric Acid Esters (R-O-S(=O)-O-R)4. Sulfuric Acid Salts (R-O-SO2-O-M)H. Thioamides (R-C(=S)-NH2)I. Thioureas (R-NH-C(=S)-NH2)J. Sulfonamides (R-SO2-NH2)VII. Oxygen Containing Compounds (Except -C(=O)-)A. Ethers1. Aliphatic Ethers (R-O-R)2. Alicyclic Ethers3. Aromatic Ethers4. Furans5. Silicon Ethers (R3-Si-O-R)6. Phosphorus Ethers ((R-O)3-P)B. Alcohols (R-OH)1. Primarya. Aliphaticb. Olefinicc. Aromatic2. Secondarya. Aliphaticb. Aromatic3. Tertiarya. Aliphaticb. Aromatic4. Diols and Polyols5. Carbohydrates6. PhenolsVIII. Compounds Containing Carbon To Oxygen Double BondsA. Ketones (R-C(=O)-R)1. Aliphatic and Alicyclic2. Olefinic3. Aromatic4. a-Diketones and b-DiketonesB. Aldehydes (R-C(=O)-H)C. Acid Halides (R-C(=O)-X)D. Anhydrides (R-C(=O)-O-C(=O)-R)E. Amides1. Primary (R-C(=O)-NH2)2. Secondary (R-C(=O)-NH-R)3. Tertiary (R-C(=O)-N-R2)F. Imides (R-C(=O)-NH-C(=O)-R)G. Hydrazides (R-C(=O)-NH-NH2)H. Ureas (R-NH-C(=O)-NH2)I. Hydantoins, Uracils, BarbituratesJ. Carboxylic Acids (R-C(=O)-OH)1. Aliphatic and Alicyclic2. Olefinic3. Aromatic4. Amino Acids5. Salts of Carboxylic AcidsK. Esters1. Aliphatic Esters of Aliphatic Acids2. Olefinic Esters of Aliphatic Acids3. Aromatic Esters of Aliphatic Acids4. Cyclic Esters (Lactones)5. Chloroformates6. Carbamates7. Esters of Phosphorus AcidsPublished by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Go to: home • ir • proton nmr • carbon nmr• mass specTable of Contents - Carbon NMRI. HydrocarbonsII. Halogenated HydrocarbonsIII. Nitrogen Containing CompoundsIV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O And P(=O)-O) VI. Sulfur Containing CompoundsVII. Oxygen Containing Compounds (Except -C(=O)-)VIII. Compounds Containing Carbon To Oxygen Double BondsI. HydrocarbonsA. Saturated Hydrocarbons1. Normal Alkanes2. Branched Alkanes3. Cyclic AlkanesB. Unsaturated Hydrocarbons1. Acyclic Alkenes2. AlkynesC. Aromatic Hydrocarbons1. Monocyclic (Benzenes) and PolycyclicII. Halogenated HydrocarbonsA. Fluorinated Hydrocarbons1. Aliphatic2. AromaticB. Chlorinated Hydrocarbons1. Aliphatic2. AromaticC. Brominated Hydrocarbons1. Aliphatic2. AromaticD. Iodinated Hydrocarbons1. Aliphatic2. AromaticIII. Nitrogen Containing CompoundsA. Amines1. Primarya. Aliphaticb. Aromatic2. Secondarya. Aliphaticb. Aromatic3. Tertiarya. Aliphaticb. AromaticB. PyridinesC. Amine SaltsD. Oximes (-CH=N-OH)E. Quaternary Ammonium SaltsF. Nitriles (-C≡N)1. Aliphatic2. Olefinic3. AromaticG. Thiocyanates (-S-C≡N)H. Nitro Compounds (-NO2)1. Aliphatic2. AromaticIV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O and P(=O)-O) VI. Sulfur Containing CompoundsA. Sulfides (R-S-R)1. Aliphatic2. AromaticB. Disulfides (R-S-S-R)C. Thiols1. Aliphatic2. AromaticD. Sulfones (R-SO2-R)VII. Oxygen Containing Compounds (Except -C(=O)-)A. Ethers1. Aliphatic Ethers (R-O-R)2. Alicyclic Ethers3. Aromatic EthersB. Alcohols (R-OH)1. Primarya. Aliphatic and Alicyclicb. Aromatic2. Secondarya. Aliphatic and Alicyclic3. Tertiarya. Aliphatic4. PhenolsVIII. Compounds Containing Carbon To Oxygen Double BondsA. Ketones (R-C(=O)-R)1. Aliphatic and Alicyclic2. AromaticB. Aldehydes (R-C(=O)-H)C. Acid Halides (R-C(=O)-X)D. Anhydrides (R-C(=O)-O-C(=O)-R)E. Amides1. Primary (R-C(=O)-NH2)2. Secondary (R-C(=O)-NH-R)3. Tertiary (R-C(=O)-N-R2)F. Carboxylic Acids (R-C(=O)-OH)1. Aliphatic and Alicyclic2. AromaticG. Esters1. Aliphatic Esters of Aliphatic Acids2. Olefinic Esters of Aliphatic Acids3. Aromatic Esters of Aliphatic AcidsPublished by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Go to: home • ir • proton nmr • carbon nmr• mass specTable of Contents - MSComing SoonI. HydrocarbonsII. Halogenated HydrocarbonsIII. Nitrogen Containing CompoundsIV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O And P(=O)-O) VI. Sulfur Containing CompoundsVII. Oxygen Containing Compounds (Except -C(=O)-)VIII. Compounds Containing Carbon To Oxygen Double BondsI. HydrocarbonsA. Saturated Hydrocarbons1. Normal Alkanes2. Branched Alkanes3. Cyclic AlkanesB. Unsaturated Hydrocarbons1. Acyclic Alkenes2. Cyclic Alkenes3. AlkynesC. Aromatic Hydrocarbons1. Monocyclic (Benzenes)2. PolycyclicII. Halogenated HydrocarbonsA. Fluorinated Hydrocarbons1. Aliphatic2. AromaticB. Chlorinated Hydrocarbons1. Aliphatic2. Olefinic3. AromaticC. Brominated Hydrocarbons1. Aliphatic2. Olefinic3. AromaticD. Iodinated Hydrocarbons1. Aliphatic and Olefinic2. AromaticIII. Nitrogen Containing CompoundsA. Amines1. Primarya. Aliphatic and Olefinicb. Aromatic2. Secondarya. Aliphatic and Olefinicb. Aromatic3. Tertiarya. Aliphatic and Olefinicb. AromaticB. PyridinesC. QuinolinesD. Miscellaneous Nitrogen HeteroaromaticsE. HydrazinesF. Amine SaltsG. Oximes (-CH=N-OH)H. Hydrazones (-CH=N-NH2)I. Azines (-CH=N-N=CH-)J. Amidines (-N=CH-N)K. Hydroxamic AcidsL. Azo Compounds (-N=N-)M. Triazenes (-N=N-NH-)N. Isocyanates (-N=C=O)O. Carbodiimides (-N=C=N-)P. Isothiocyanates (-N=C=S)Q. Nitriles (-C≡N)1. Aliphatic2. Olefinic3. AromaticR. Cyanamides (=N-C≡N)S. Thiocyanates (-S-C≡N)T. Nitroso Compounds (-N=O)U. N-Nitroso Compounds (=N-N=O)V. Nitrites (-O-N=O)W. Nitro Compounds (-NO2)1. Aliphatic2. AromaticX. N-Nitro-Compounds (=N-NO2)IV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O and P(=O)-O) VI. Sulfur Containing CompoundsA. Sulfides (R-S-R)1. Aliphatic2. Heterocyclic3. AromaticB. Disulfides (R-S-S-R)C. Thiols1. Aliphatic2. AromaticD. Sulfoxides (R-S(=O)-R)E. Sulfones (R-SO2-R)F. Sulfonyl Halides (R-SO2-X)G. Sulfonic Acids (R-SO2-OH)1. Sulfonic Acid Salts (R-SO2-O-M)2. Sulfonic Acid Esters (R-SO2-O-R)3. Sulfuric Acid Esters (R-O-S(=O)-O-R)H. Thioamides (R-C(=S)-NH2)I. Thioureas (R-NH-C(=S)-NH2)J. Sulfonamides (R-SO2-NH2)K. Sulfamides (R-NH-SO2-NH-R)VII. Oxygen Containing Compounds (Except -C(=O)-)A. Ethers1. Aliphatic Ethers (R-O-R)2. Acetals (R-CH-(-O-R)2)3. Alicyclic Ethers4. Aromatic Ethers5. Furans6. Silicon Ethers (R3-Si-O-R)7. Phosphorus Ethers ((R-O)3-P)8. Peroxides (R-O-O-R)B. Alcohols (R-OH)1. Primarya. Aliphatic and Alicyclicb. Olefinicc. Aromaticd. Heterocyclic2. Secondarya. Aliphatic and Alicyclicb. Olefinicc. Aromatic3. Tertiarya. Aliphaticb. Olefinicc. Aromatic4. Diols5. Carbohydrates6. PhenolsVIII. Compounds Containing Carbon To Oxygen Double BondsA. Ketones (R-C(=O)-R)1. Aliphatic and Alicyclic2. Olefinic3. Aromatic4. α-Diketones and β-DiketonesB. Aldehydes (R-C(=O)-H)C. Acid Halides (R-C(=O)-X)D. Anhydrides (R-C(=O)-O-C(=O)-R)E. Amides1. Primary (R-C(=O)-NH2)2. Secondary (R-C(=O)-NH-R)3. Tertiary (R-C(=O)-N-R2)F. Imides (R-C(=O)-NH-C(=O)-R)G. Hydrazides (R-C(=O)-NH-NH2)H. Ureas (R-NH-C(=O)-NH2)I. Hydantoins, Uracils, BarbituratesJ. Carboxylic Acids (R-C(=O)-OH)1. Aliphatic and Alicyclic2. Olefinic3. Aromatic4. Amino Acids5. Salts of Carboxylic AcidsK. Esters1. Aliphatic Esters of Aliphatic Acids2. Olefinic Esters of Aliphatic Acids3. Aliphatic Esters of Olefinic Acids4. Aromatic Esters of Aliphatic Acids5. Esters of Aromatic Acids6. Cyclic Esters (Lactones)7. Chloroformates8. Esters of Thio-Acids9. Carbamates10. Esters of Phosphorus AcidsPublished by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Go to: home • ir • proton nmr • carbon nmr• mass specSaturated HydrocarbonsNormal Alkanes1. C-H stretching vibration:CH3 asymmetric stretching, 2972-2952 cm-1CH3 symmetric stretching, 2882-2862 cm-1CH2 asymmetric stretching, 2936-2916 cm-1CH2 symmetric stretching, 2863-2843 cm-12. C-H bending vibration:CH3 asymmetric bending, 1470-1430 cm-1CH2 asymmetric bending, 1485-1445 cm-1(overlaps band due to CH3 asymmetricbending)3. C-H bending vibration:CH3 symmetric bending, 1380-1365 cm-1(when CH3 is attached to a C atom)4. C-H wagging vibration:CH2 out-of-plane deformations wagging, 1307-1303 cm-1 (weak) 5. CH2 rocking vibration:(CH2)2 in-plane deformations rocking, 750-740 cm-1(CH2)3 in-plane deformations rocking, 740-730 cm-1(CH2)4 in-plane deformations rocking, 730-725 cm-1(CH2) ≥ 6 in-plane deformations rocking, 722 cm-1Splitting of the absorption band occurs in most cases (730 and 720 cm-1) when the long carbon-chain alkane is in the crystalline state (orthorombic or monoclinic form).Coming Soon!Click on a vibrational mode link in the table to the leftor the spectrum above to visualize the vibrational mode here.Published by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Saturated HydrocarbonsBranched Alkanes1. C-H stretching vibration:CH3 asymmetric stretching, 2972-2952 cm-1CH3 symmetric stretching, 2882-2862 cm-1CH2 asymmetric stretching, 2936-2916 cm-1CH2 symmetric stretching, 2863-2843 cm-12. C-H bending vibration:CH3 asymmetric bending, 1470-1430 cm-1CH2 asymmetric bending, 1485-1445 cm-1(overlaps band due to CH3 symmetric bending)3. C-H bending vibration:-C-C(CH3)-C-C- symmetric bending, 1380-1365 cm-1(when CH3 is attached to a C atom)-C-C(CH3)-C(CH3)-C-C- symmetric bending, 1380-1365 cm-1(when CH3 is attached to a C atom)(CH3)2CH- symmetric bending, 1385-1380 cm-1and 1365 cm-1(two bands of about equal intensity)-C-C(CH3)2-C- symmetric bending,1385-1380 cm-1and 1365 cm-1 (two bands of about equal intensity).(CH3)3C- symmetric bending, 1395-1385 cm-1and 1365 cm-1(two bands of unequal intensity with the 1365 cm-1 band as the much stronger component of the doublet).4. Skeletal vibration:-C-C(CH3)-C-C-,1159-1151cm-1-C-C(CH3)-C(CH3)-C-C-,1130-1116 cm-1(CH3)CH-,1175-1165 cm-1 and 1170-1140 cm-1-C-C(CH3)2-C-,1192-1185 cm-1(CH3)3C-, 1255-1245 cm-1 and 1250-1200 cm-15. C-H rocking vibration:(CH2)2 in-plane deformations rocking, 750-740 cm-1(CH2)3 in-plane deformations rocking, 740-730 cm-1(CH2)4 in-plane deformations rocking, 730-725 cm-1(CH2) ≥ 6 in-plane deformations rocking, 722 cm-1Coming Soon!Click on a vibrational mode link in the table to the left or the spectrum above to visualize the vibrational modehere.Published by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Saturated Hydrocarbons Cyclic AlkanesCyclopropanes1. C-H stretching vibration:ring CH 2 asymmetric stretching, 3100-3072 cm -1 ring CH 2 symmetric stretching, 3030-2995 cm -12. Ring deformation vibration:ring deformation, 1050-1000 cm -13. C-H deformation vibration: CH 2 wagging, 860-790 cm -1Cyclobutanes1. C-H stretching vibration:ring CH 2 asymmetric stretching, 3000-2974 cm -1 ring CH 2 symmetric stretching, 2925-2875 cm -12. C-H deformation vibration:ring CH 2 asymmetric bending, ca 1444 cm -13. Ring deformation vibration:ring deformation, 1000-960 cm -1 888-838 cm -14. C-H deformation vibration:ring CH 2 rocking, 950-900 cm -1Cyclopentanes1. C-H stretching vibration:ring CH 2 asymmetric stretching, 2960-2952 cm -1 ring CH 2 symmetric stretching, 2866-2853 cm -1 2. C-H deformation vibration:ring CH 2 asymmetric bending, ca 1455 cm -1 3. Ring deformation vibration:ring deformation, 1000-960 cm -1 4. C-H deformation vibration:ring CH 2rocking, 930-890 cm -1Cyclohexanes1. C-H stretching vibration:ring CH 2 asymmetric stretching, ca 2927 cm -1ring CH 2 symmetric stretching, ca 2854 cm -1 2. C-H deformation vibration:ring CH 2 asymmetric bending, ca 1462 cm -1 3. C-H deformation vibration:ring CH 2 wagging, ca 1260 cm -1 4. Ring deformation vibration:ring deformation, 1055-1000 cm -1 1000- 952 cm -1 5. C-H deformation vibration:ring CH 2 rocking, 890-860 cm -16. The spectra of cyclic alkanes of five or more ring carbons show ring CH 2 stretching frequencies which overlap those of CH 3 and CH 2 groups of their alkyl substituents. These frequencies also overlap thoseof the CH 3 and CH 2 stretching frequencies of acylic alkanes. When samples of unknown composition are examined for the presence of such ring structures, the absorption bands of their spectra at the C-H stretching region should havethe best possible resolution.Coming Soon!Click on a vibrational mode link in the table to the left or the spectrum above to visualize the vibrational modehere.Numerous references cite the spectral region of 2800-2600 cm-1 for obtainingconfirmatory evidence of the presence of saturated simple ring structures. Absorptionat this region consists of a weak band or bands whose pattern and band locations arehelpful in confirming or indicating the presence of these rings. Although such absorptionfeatures have a limited diagnostic value, it is most reliable when the absorption occursin the spectra of simple saturated aliphatic hydrocarbons.Cycloalkanes (8, 9, and 10 C atoms)1 C-H stretching vibration:ring CH2 asymmetric stretching, ca 2930 cm-1ring CH2 symmetric stretching, ca 2850 cm-12. C-H deformation vibration:ring CH2 asymmetric bending, 2 or 3 absorption bands,1487-1443 cm-1Published by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Go to: home • ir • proton nmr • carbon nmr• mass specUnsaturated HydrocarbonsAcyclic AlkenesMonosubstituted Alkenes (vinyl)1. C=C stretching vibration:C=C stretching, 1648-1638 cm-12. C-H deformation vibration:trans CH wagging, 995-985 cm-1CH2 wagging, 910-905 cm-13. C-H stretching vibration:CH2 asymmetric stretching, 3092-3077 cm-1CH2 symmetric stretching and CH stretching, 3025-3012 cm-1 4. C-H deformation vibration:CH2 asymmetric bending, 1420-1412 cm-15. C-H deformation vibration overtone:overtone of CH2 wagging, 1840-1805 cm-1Asymmetric Disubstituted Alkenes (vinylidine)1. C=C stretching vibration:C=C stretching, 1661-1639 cm-12. C-H deformation vibration:CH2 wagging, 895-885 cm-13. C-H stretching vibration:CH2 stretching asymmetric, 3100-3077 cm-14. C-H deformation vibration overtone:overtone of CH2 wagging, 1792- 1775 cm-1Symmetric Disubstituted Alkenes (cis)1. C=C stretching vibration:C=C stretching, 1662- 1631 cm-12. C-H deformation vibration:cis CH wagging, 730- 650 cm-13. C-H stretching vibration:CH stretching, 3050-3000 cm-1Symmetric Disubstituted Alkenes (trans)1. C=C stretching vibration:C=C stretching, ca 1673 cm-1, very weak or absent2. C-H deformation vibration:trans CH wagging, 980-965 cm-13. C-H stretching vibration:CH stretching, 3050-3000 cm-1Trisubstituted Alkenes1. C=C stretching vibration:C=C stretching, 1692-1667 cm-12. C—H deformation vibration:C-H wagging, 840-790 cm-13. C-H stretching vibration:C-H stretching, 3050-2990 cm-1Coming Soon!Click on a vibrational mode link in the table to the left or the spectrum above to visualize the vibrational modehere.Tetrasubstituted Alkenes1. C=C stretching vibration:C=C stretching, 1680-1665 cm-1, very weak or absentNOTES: The C=C stretching vibration of molecules which maintain acenter of symmetry absorbs very weakly, if at all, in the infrared region and,usually, is difficult to detect. This is true of the trans isomers and thetetrasubstitutedC=C linkages.When two or more olefinic groups occur in the hydrocarbon molecule, the infraredabsorption spectrum shows the additive and combined absorption of theunsaturatedgroups. However, if the unsaturated groups are subject to conjugation, the C=Cstretchingfrequency, usually, is lowered and a splitting of the C=C stretching frequencyband occurs.Conjugation also intensifies the C=C stretching frequency of trans unsaturatedgroups.Published by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Go to: home • ir • proton nmr • carbon nmr• mass specUnsaturated Hydrocarbons Cyclic AlkenesEndocyclic C=CEndocyclic C=C corresponds to cis symmetrically disubstituted C=C of acyclic alkenes.1. C=C stretching, vibration:C=C stretching, near 1650 cm -1(except cyclobutene, 1560 cm -1 and cyclopentene, 1611 cm -1)2. C-H deformation vibration: CH wagging, 730- 650 cm -13. C-H stretching vibration:CH stretching, 3075- 3010 cm -1(usually two bands, asymmetric stretching and symmetric stretching for 4, 6, 7, and 8 membered rings)1- substituted endocyclic C=C1- substituted endocyclic C=C corresponds to trisubstituted acyclic alkenes.1. C=C stretching vibration:C=C stretching, near 1650 cm -1 (frequency raised)2. C-H deformation vibration: CH wagging, 840-790 cm -13. C-H stretching vibration:CH stretching, near 3000 cm -11.2- disubstituted endocyclic C=C1. C=C stretching vibration:C=C stretching, 1690-1670 cm -1 (4, 5, and 6 membered rings)Exocyclic C=CH 2Exocyclic C=CH 2 corresponds to the asymmetrically disubstituted C=C of acyclic alkenes (vinylidine).1. C=C stretching,1678-1650 cm -1 (4, 5, and 6 membered rings)2. C-H deformation vibration:=CH 2 wagging, 895-885 cm -13. C-H stretching vibration:=CH 2 stretching, near 3050 cm -1NOTES: The C=C stretching frequency of both the endocyclic HC=CH and the exocyclic C=CH 2 is sensitive to ring strain. As the ring size decreases from 6 to 4 members, the C=C stretching frequency of the endocyclic HC=CH is lowered. However, for the C=C stretching frequency of exocyclic C=CH 2, a gradual increase in the C=C stretching frequency occurs as the ring gets smaller. Substitution of methyl groups for the hydrogens of the endocyclic HC=CH and the exocyclic C=CH 2 cause an increase in the C=C stretching frequency.When two or more C=C groups occur in the hydrocarbon molecule, the infrared absorption spectrum shows the additive and combined absorption effects of the unsaturated groups. If such groups are subject to conjugation, the C=C stretching frequency is lowered and asplitting of the C=C stretching frequency band occurs.Coming Soon!Click on a vibrational mode link in the table to the left or the spectrum above to visualize the vibrational modehere.Published by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Unsaturated Hydrocarbons AlkynesMonosubstituted Alkynes (RC ≡CH)1. C ≡C stretching vibration:C ≡C stretching, 2140-2100 cm -12. C-H stretching vibration:≡CH bending, ca 3300 cm -13. C-H deformation vibration: ≡CH bending, 642-615 cm -14. C-H deformation vibration overtone:overtone of ≡CH deformation, 1260-1245 cm -1Disubstituted Alkynes (RC ≡CR')1. C ≡C stretching vibration:C ≡C stretching, 2260-2190 cm -1 (unconjugated)NOTES: Although the intensity of the absorption band caused bythe C ≡C stretching vibration is variable, it is strongest when the alkyne group is monosubstituted. When this group is disubstituted in open chain compounds, the intensity of the C ≡C stretching vibration band diminishesas its position in the molecule tends to establish a pseudo center of symmetry. In some instances this band is too weak to be detected and, thus, its absence in the spectrum does not, necessarily, establish proof of the absence of this linkage.Occasionally, the spectra of disubstituted alkynes show two or more bands at the C ≡C stretching region.Conjugation with olefinic double bonds or aromatic rings tend to slightly increase the intensity of the C ≡C stretching vibration band and shift it toa lower frequency.Coming Soon!Click on a vibrational mode link in the table to the left or the spectrum above to visualize the vibrational modehere.Published by Bio-Rad Laboratories, Inc., Informatics Division . © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.。

微波灰化-电感耦合等离子体发射光谱法测定婴幼儿乳粉中的钙和磷

微波灰化-电感耦合等离子体发射光谱法测定婴幼儿乳粉中的钙和磷

第 29 卷第 4 期分析测试技术与仪器Volume 29 Number 4 2023年12月ANALYSIS AND TESTING TECHNOLOGY AND INSTRUMENTS Dec. 2023分析测试经验介绍(407 ~ 413)微波灰化-电感耦合等离子体发射光谱法测定婴幼儿乳粉中的钙和磷陈丽梅,张 慧,白国涛,马彩霞,姚思雨,王 婧(呼和浩特海关技术中心,内蒙古呼和浩特 010020)摘要:采用微波灰化-电感耦合等离子体发射光谱法(ICP-OES)测定婴幼儿乳粉中钙、磷元素含量. 采用微波灰化法对婴幼儿乳粉进行前处理,正交试验方法确定微波灰化最佳条件,灰化后产物用2 mL硝酸溶液(体积比为1∶1)溶解后,用ICP-OES对钙、磷元素进行含量检测. 磷加标回收率为86%~104%,钙加标回收率为87%~96%.磷的相对标准偏差为2.5%~7.0%,钙的相对标准偏差为3.9%~10.0%,能够满足日常检测要求. 采用微波灰化法对婴幼儿乳粉中钙、磷元素进行样品前处理,相比微波消解方法,具有用时短、用酸量少、消解效果好、不需要进行赶酸处理等优点. 与干法灰化和湿法消解相比大大减少了样品处理时间. 采用微波灰化与ICP-OES结合对婴幼儿乳粉中的重要指标元素进行检测,在婴幼儿乳粉质量控制中有很好的应用价值.关键词:微波灰化;电感耦合等离子体发射光谱法;婴幼儿乳粉;钙;磷中图分类号:O657. 31 文献标志码:B 文章编号:1006-3757(2023)04-0407-07DOI:10.16495/j.1006-3757.2023.04.010Detemination of Calcium and Phosphorus in Infant Formula by Microwave Ashing- Inductive Coupled Plasma Emission SpectrometryCHEN Limei, ZHANG Hui, BAI Guotao, MA Caixia, YAO Siyu, WANG Jing(Technology Center of Hohhot Custom, Hohhot 010020, China)Abstract:The microwave ashing-inductive coupled plasma emission spectrometry (ICP-OES ) was used to determine the content of calcium and phosphorus in infant formula. The method of microwave ashing was used to pretreatment of the infant formula. The optimization conditions were determined by orthogonal test. After the microwave ashing, the ashes were dissolved with 2 mL nitric acid solution (volume ratio was 1∶1). The ICP-OES was used to determine the content of calcium and phosphorus. The recoveries of phosphorus and calcium were 86%~104% and 87%~96%, respectively. The relative standard deviation of phosphorus and calcium were 2.5%~7.0% and 3.9%~10.0%, respectively, which could meet the detection requirements. Compared with the method of microwave digestion, microwave ashing has the advantages of shorter time, less acid, better digestion effect and no need to drive acid treatment for calcium and phosphorus in infant formula. Compared with wet digestion and dry ashing, the sample processing time was greatly reduced. The detection of important index elements in infant formula by microwave ashing combined with ICP-OES has a good application value in the quality control of infant formula.Key words:microwave ashing;ICP-OES;infant formula;calcium;phosphorus收稿日期:2023−10−09; 修订日期:2023−12−12.基金项目:海关总署科研项目(批准号:2021HK186)[The Research Project of General Administration of Customs (2021HK186)]作者简介:陈丽梅(1981−),女,高级工程师,主要从事食品中元素检测工作,E-mail:******************.微波灰化技术是一种创新的样品前处理方法,利用抗热的密闭腔体及微波技术来加热,使得灰化速度提高,减少了能量损耗,增加了样品的处理量,工作环境清洁,使用安全. 不同于湿法酸消解,微波灰化的优点是处理过程比较简单,实验室日常工作非常通用,多用于过程及质量控制. 在石油工业、制药业、食品工业、塑料制品制造业、污染物治理等领域都有着广泛的应用. 微波灰化的原理是微波系统发射均匀的微波,穿透高温泡沫陶瓷护体,内置的耐高温泡沫瓷体内的碳化硅板将微波能量转化为热能,热量直接辐射到样品内,样品被均匀加热.微波的使用大大增加了加热效率,相较于传统马弗炉,加热速度大幅提高. 同时,微波灰化消解用酸量也非常小,既节约了酸的使用量,又减少了赶酸过程对环境的污染. 微波灰化消解法在元素检测前处理中主要应用于油料油品[1-5]、塑料 [6-7]、傣药[8]、食用菌[9]、小麦淀粉[10-11]、电泳材料[12]等样品.钙、磷都是人体必须的营养元素. 在人体吸收代谢过程中,钙和磷会相互影响. 根据GB 10765—2021《食品安全国家标准婴儿配方食品》[13]和GB 10767—2021《食品安全国家标准幼儿配方食品》[14]要求,钙磷元素比值范围分别为1∶1~2∶1和1.2∶1~2∶1,如果婴幼儿乳粉中钙磷比例失衡,婴幼儿对钙的有效吸收就会降低,造成膳食中钙营养元素的相对缺乏,影响骨骼和牙齿的发育,因此对婴幼儿乳粉中钙、磷元素进行检测十分必要.目前婴幼儿乳粉前处理方法主要有微波消解[13]、干法灰化[14]、高压罐消解[15]和湿法消解[16]. 国内未见微波灰化法在乳粉前处理中的应用研究. 由于乳粉基质比较复杂,添加物质较多,用传统的前处理方法对乳粉进行消解,有消解时间长、使用酸量大等不足. 本文以微波灰化为前处理方法,结合电感耦合等离子体发射光谱仪(ICP-OES)检测婴幼儿乳粉中钙、磷元素的含量,建立一种用时短、用酸量少的测定乳粉中钙、磷元素含量的检测方法.1 试验部分1.1 仪器与试剂电感耦合等离子体发射光谱仪(720型,安捷伦科技,美国),微波灰化仪(CEM,培安科技,美国),电子天平(Sartorius,塞多利斯公司,德国)(感量:0.001 g),瓷坩埚(50 mL). 硝酸(默克,优级纯),钙、磷标准溶液1 000 mg/L(中国计量科学研究院). 试验过程中所使用婴幼儿乳粉均购自超市,样品编号1、2、5样品为婴幼儿1段乳粉,样品编号3、4为纯奶粉,样品编号6为婴幼儿2段乳粉,样品编号7样品为婴幼儿3段乳粉. 试验过程中使用水均为去离子水. 所有使用的器具使用前均经20%硝酸浸泡过夜.1.2 试验方法1.2.1 标准溶液配制分别吸取钙、磷标准溶液1.0、2.0、3.0、4.0、5.0 mL于100.0 mL容量瓶中,使用2%硝酸定容至刻度,所配制溶液质量浓度分别为10、20、30、40、50 mg/L.硝酸溶液(硝酸∶水体积比为1∶1)配制:量取100 mL硝酸加入至100 mL去离子水中,混合均匀.1.2.2 试验方案在瓷坩埚中称量0.500 g乳粉,设定微波灰化程序进行试验,灰化完成后待微波灰化炉温冷却至150 ℃以下取出坩埚,晾至室温,用2.0 mL硝酸溶液(硝酸∶水体积比为1∶1)溶解灰分,将溶液转移至100.0 mL容量瓶中,用水清洗瓷坩埚,将清洗液转移至容量瓶中,用去离子水定容至刻度,混合均匀后进行钙、磷元素含量测定.1.3 ICP-OES仪器条件ICP-OES检测条件:功率1.2 kW,等离子体气气体流量:15.0 L/min,辅助器流量:1.50 L/min,雾化器流量:0.75 L/min,读数时间:1 s,进样时间:15 s,稳定时间:15 s. 各元素检测波长分别为钙317.933 nm、磷213.618 nm.1.4 微波灰化条件优化方案采用正交试验法对微波灰化条件进行优化,选取4因素4水平正交试验表,因素和水平如表1所列.表 1 正交试验的因素和水平Table 1 Factors and levels of orthogonal test因素因素A(灰化温度)/℃因素B(灰化时间)/min因素C(碳化温度)/℃因素D(碳化时间)/min 水平1450152002水平2500302504水平3550603008水平46009035012408分析测试技术与仪器第 29 卷2 结果与讨论2.1 微波灰化参数优化采用正交试验法对微波灰化的各个参数进行优化. 正交试验方案及结果如表2所列,正交试验结果分析如表3所列.从表3可以看出,磷元素4个因素极差从大到小的顺序为:A>C>B>D,钙元素4个因素极差从大到小的顺序为:A>B>C>D,因此灰化温度在整个灰化过程中起到重要的作用,碳化时间因素影响最小.2.1.1 微波灰化温度的优化正交试验因素的极差结果越大,代表该因素在试验条件中影响较大. 从正交试验极差分析结果可以看出,微波灰化温度极差最大,是影响灰化的最主要因素. 将微波灰化温度各个水平对应的k值为纵坐标,灰化温度为横坐标作因素水平图,如图1(a)所示. 从图1(a)可以看出,当灰化温度达到500 ℃时,钙和磷随着微波灰化温度的提高,所得到的含量没有明显的增加. 钙、磷两种元素最佳微波灰化温度虽然有所差别,但是差别不大. 综合以上结果,选择500 ℃作为微波灰化的最优温度.2.1.2 微波碳化温度的优化从表3可以看出,碳化温度是灰化效果的次主要因素. 碳化过程是将待处理的样品置于低温下使表 2 微波灰化正交试验方案及试验结果Table 2 Orthogonal test programs and results ofmicrowave ashing方案编号试验方案试验结果/(mg/kg)灰化温度/℃灰化时间/min碳化温度/℃碳化时间/min磷钙1450152002 2 605 3 514 2500153508 2 489 3 338 35501525012 2 545 3 411 4600153004 2 638 3 574 54503035012 2 199 2 928 6500302004 2 625 3 532 7550303002 2 615 3 504 8600302508 2 617 3 513 9450602504 2 490 3 334 105006030012 2 710 3 645 11550602008 2 542 3 414 12600603502 2 545 3 451 134******** 2 544 3 392 14500902502 2 650 3 565 155******** 2 721 3 664 166009020012 2 636 3 625表 3 灰化参数优化正交试验结果分析Table 3 Results analysis of orthogonal test/(mg/kg)元素 因素A因素B因素C因素D元素 因素A因素B因素C因素D 磷K19 83810 27710 40810 415钙K113 16813 83714 08514 034 K210 4741005610 30210 474K214 08013 47713 82314 104K310 4231028710 50710 192K313 99313 84414 11513 657K410 43610 5519 95410 090K414 16314 24613 38113 609k1 2 459 2 569 2 602 2 604k1 3 292 3 459 3 521 3 509k2 2 618 2 514 2 576 2 619k2 3 520 3 369 3 456 3 526k3 2 606 2 572 2 627 2 548k3 3 498 3 461 3 529 3 414k4 2 609 2 638 2 488 2 522k4 3 541 3 562 3 345 3 402极差159********极差249193184124极差顺序:A>C>B>D极差顺序:A>B>C>D最优水平:A2B4C3D2最优水平:A4B4C3D2注:K1、K2、K3、K4表示任意列上水平1、水平2、水平3、水平4所对应的试验结果之和;k1、k2、k3、k4表示水平1、水平2、水平3、水平4对应试验结果均值第 4 期陈丽梅,等:微波灰化-电感耦合等离子体发射光谱法测定婴幼儿乳粉中的钙和磷409其碳化,减少因温度上升过快而使得样品灰分的挥发. 以微波灰化碳化温度各个水平对应k 值为纵坐标,碳化温度为横坐标作因素水平图,如图1(b )所示.从图1(b )可以看出,过高的碳化温度并不利于微波灰化的结果. 随着碳化温度的提高,样品碳化过程过快,使得元素随着碳化的烟雾挥出,造成了元素含量的损失. 当碳化温度为300 ℃时,钙和磷含量均达到最佳水平. 因此选择最佳的碳化温度为300 ℃.2.1.3 微波灰化时间的优化以微波灰化时间各个水平对应k 值为纵坐标,微波灰化时间为横坐标作因素水平图,如图1(c )所示.从图1(c )中可看到并没有最优的灰化时间点出现,因此对微波灰化时间进行了单点优化,结果如图1(d)所示. 从图1(d) 中可以看出,当灰化时间达到90 min 后,延长灰化时间对于消解并没有明显的改善,综合考虑各元素的灰化时间,选择最优的灰化时间为90 min.2.1.4 碳化时间的优化以碳化时间各个水平对应k 值为纵坐标,碳化时间为横坐标作因素水平图,结果如图2所示. 从图2可以看出,当碳化时间达到4 min 时,钙和磷的含量水平达到最优,因此所选碳化时间为4 min.2.1.5 称样量的优化通过正交试验结果,选择最佳微波灰化条件:微波灰化温度500 ℃,灰化时间90 min ,碳化温度300 ℃,碳化时间4 min. 在最优的条件下对不同称样量(0.2、0.5、1.0、2.0、3.0 g )样品进行前处理,采用ICP-OES 对其含量进行检测,以样品含量为纵坐标,样品称样量为横坐标作图3. 当称样量达到2.0 g 时,婴幼儿乳粉出现了灰化不完全的情况,定容样品中含有黑色沉淀. 从图3也可以看出,当称2 0002 5003 0003 5004 000元素质量分数/(m g /k g )T /℃1 5002 0002 5003 0003 5004 000T /℃元素质量分数/(m g /k g )1 5002 0002 5003 0003 5004 000元素质量分数/(mg /k g )t /min2 0002 5003 0003 5004 0004 5005 000元素质量分数/(m g /k g )t /min图1 (a )灰化温度、(b )碳化温度、(c )微波灰化时间的因素水平图、(d )微波灰化时间的单点优化Fig. 1 Factor level diagrams of (a) microwave ashing temperatures, (b) microwave carbonization temperatures and(c) microwave ashing times, (d) optimization of microwave ashing times1 5002 0002 5003 0003 5004 000元素质量分数/(m g /k g )t /min图2 碳化时间的因素水平图Fig. 2 Factor level diagram of microwave carbonizationtimes410分析测试技术与仪器第 29 卷样量达到2.0 g 时,检测到的样品含量出现下降的趋势,这是由于样品称样量过多时,样品没有被完全灰化,待测元素无法完全转移到溶液中,造成检测含量降低. 因此最佳称样量应小于2.0 g.2.2 各元素仪器方法学考察采用外标法对各元素进行检测,以元素浓度(X )为横坐标,元素在ICP-OES 检测强度(Y )为纵坐标拟合线性方程,得到线性方程和相对标准偏差(RSD ). 各元素检出限取3倍样品空白标准偏差(n =11)计算,定量限取10倍样品空白标准偏差(n =11)计算. 所得结果如表4所列.表 4 线性方程、检出限和定量限Table 4 Linear regression equations, limits of detection and limits of quantitation元素线性方程线性范围/(mg/L )相关系数RSD/%检出限/(mg/L )定量限/(mg/L )钙Y =37 341.809 + 55 064.512X 0~500.9990.860.023 70.079磷Y =602.582 + 1 742.811X0~500.9990.750.022 50.0752.3 加标回收试验在婴幼儿乳粉中添加标准溶液,采用最优灰化条件进行样品处理后采用ICP-OES 进行检测,结果如表5所列. 从表5可以看出,磷元素加标回收率为86%~104%,钙元素加标回收率为87%~96%. 磷和钙元素6次加标回收率的RSD 分别为2.5%~7.0%,3.9%~10.0%. 加标回收率结果能够满足日常检测要求.表 5 加标回收率Table 5 Results of recovery元素背景/(mg/kg)添加质量分数/(mg/kg)测得质量分数/(mg/kg)加标回收率/%RSD/(%,n =6)磷2 582500 3 0911027.01 000 3 623104 4.22 0004 30386 2.5钙4 1771 0005 0478710.02 0006 01792 4.73 0007 057963.92.4 实际样品的检测采用所建立的方法对市场采购的婴幼儿乳粉进行钙、磷元素含量测定,测定结果如表6所列. 从表中可以看出,所检测的样品编号1、2、5号样品钙磷比值分别为1.4、1.6、1.6,符合GB 10765—2021《食品安全国家标准 婴儿配方食品》[13]要求. 样品编号3、4 号样品是纯奶粉和甜奶粉,钙磷比值分别为1.2和1.1. 样品编号6、7号样品比值分别为1.7、1.3,符合GB 10767—2021《食品安全国家标准 幼儿配方食品》[14]要求.2.5 微波灰化与其他消解方法的比较将微波灰化法与其他前处理方法消解体系和所用时间进行比较,结果如表7所列. 微波灰化前处理方法的精密度和回收率能够满足日常检测的需求. 与干法灰化相比,由于微波的使用,大大增加了加热效率,从而使在进行婴幼儿乳粉前处理过程m /g1 5002 0002 5003 0003 5004 0004 500元素质量分数/(m g /k g )图3 样品称样量的选择Fig. 3 Optimization of sample weights第 4 期陈丽梅,等:微波灰化-电感耦合等离子体发射光谱法测定婴幼儿乳粉中的钙和磷411中所需要的灰化时间更短,总体处理时间与微波消解相当. 微波灰化前处理只需要在灰化完成后用少量酸溶解样品,因此用酸量与湿法消解相比更少.说明微波灰化用于婴幼儿乳粉中钙、磷检测的前处理,所用时间少,消解所用到的酸的种类和剂量也很少,减少了酸的使用对于实验环境和实验人员的危害.3 结论采用微波灰化对婴幼儿乳粉中钙、磷元素进行样品前处理,相比微波消解方法,具有用时短、用酸量少、消解效果好、不需要进行赶酸处理等优势. 与干法灰化和湿法消解相比大大减少了样品处理时间. 采用微波灰化与ICP-OES 结合对婴幼儿乳粉中重要的指标元素钙、磷元素进行检测,是一种快速、环保、准确度高的方法,在婴幼儿乳粉质量控制中有很好的应用价值.参考文献:俞晔, 乙小娟, 刘一军. 微波灰化-原子荧光光谱法测定植物油中砷[J ]. 现代科学仪器,2002(6):48-50.[YU Ye, YI Xiaojuan, LIU Yijun. 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[ZHANG Hui, XIA Yongjun.Determination of trace lead in exported wheat starch by microwave ashing-hydride generation-atomic fluor-escence spectrometry [J ]. Chinese Journal of Spectro-scopy Laboratory ,2005,22 (3):559-563.][ 10 ]李旭, 吴维吉, 刘佳, 等. 微波灰化电感耦合等离子体质谱法测定小麦中6种金属元素含量[J ]. 食品安全质量检测学报,2019,10(4):866-869. [LI Xu, WU Weiji, LIU Jia, et al. Determination of 6 kinds of met-al elements in wheat by microwave ashing and induct-ively coupled plasma-mass spectrometry [J ]. Journal[ 11 ]of Food Safety & Quality ,2019,10 (4):866-869.]吴志刚, 曹璨. 微波灰化-电感耦合等离子体质谱法测定电泳涂料中15种金属元素[J ]. 化学分析计量,2023,32(1):6-10. [WU Zhigang, CAO Can. Determ-ination of fifteen elements in electrophoretic coating by microwave ashing-inductively coupled plasma mass spectrometry [J ]. 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Cosmology with High-redshift Galaxy Survey Neutrino Mass and Inflation

Cosmology with High-redshift Galaxy Survey Neutrino Mass and Inflation

a r X i v :a s t r o -p h /0512374v 3 5 J u n 2006Cosmology with High-redshift Galaxy Survey:Neutrino Mass and InflationMasahiro Takada 1,Eiichiro Komatsu 2and Toshifumi Futamase 11Astronomical Institute,Tohoku University,Sendai 980-8578,Japan and 2Department of Astronomy,The University of Texas at Austin,Austin,TX 78712High-z galaxy redshift surveys open up exciting possibilities for precision determinations of neu-trino masses and inflationary models.The high-z surveys are more useful for cosmology than low-z ones owing to much weaker non-linearities in matter clustering,redshift-space distortion and galaxy bias,which allows us to use the galaxy power spectrum down to the smaller spatial scales that are inaccessible by low-z surveys.We can then utilize the two-dimensional information of the linear power spectrum in angular and redshift space to measure the scale-dependent suppression of matter clustering due to neutrino free-streaming as well as the shape of the primordial power spectrum.To illustrate capabilities of high-z surveys for constraining neutrino masses and the primordial power spectrum,we compare three future redshift surveys covering 300square degrees at 0.5<z <2,2<z <4,and 3.5<z <6.5.We find that,combined with the cosmic microwave background data expected from the Planck satellite,these surveys allow precision determination of the total neutrino mass with the projected errors of σ(m ν,tot )=0.059,0.043,and 0.025eV,respectively,thus yielding a positive detection of the neutrino mass rather than an upper limit,as σ(m ν,tot )is smaller than the lower limits to the neutrino masses implied from the neutrino oscillation experiments,by up to a factor of 4for the highest redshift survey.The accuracies of constraining the tilt and running index of the primordial power spectrum,σ(n s )=(3.8,3.7,3.0)×10−3and σ(αs )=(5.9,5.7,2.4)×10−3at k 0=0.05Mpc −1,respectively,are smaller than the current uncertainties by more than an or-der of magnitude,which will allow us to discriminate between candidate inflationary models.In particular,the error on αs from the future highest redshift survey is not very far away from the prediction of a class of simple inflationary models driven by a massive scalar field with self-coupling,αs =−(0.8−1.2)×10−3.PACS numbers:95.55.Vj,98.65.Dx,98.80.Cq,98.70.Vc,98.80.EsI.INTRODUCTIONWe are living in the golden age of cosmology.Vari-ous data sets from precision measurements of tempera-ture and polarization anisotropy in the cosmic microwave background (CMB)radiation as well as those of matter density fluctuations in the large-scale structure of the universe mapped by galaxy redshift surveys,Lyman-αforests and weak gravitational lensing observations are in a spectacular agreement with the concordance ΛCDM model [1,2,3,4].These results assure that theory of cos-mological linear perturbations is basically correct,and can accurately describe the evolution of photons,neu-trinos,baryons,and collisionless dark matter particles [5,6,7],for given initial perturbations generated during inflation [8,9].The predictions from linear perturbation theory can be compared with the precision cosmological measurements,in order to derive stringent constraints on the various basic cosmological parameters.Future obser-vations with better sensitivity and higher precision will continue to further improve our understanding of the uni-verse.Fluctuations in different cosmic fluids (dark matter,photons,baryons,and neutrinos)imprint characteristic features in their power spectra,owing to their interac-tion properties,thermal history,equation of state,and speed of sound.A remarkable example is the acoustic oscillation in the photon-baryon fluid that was generated before the decoupling epoch of photons,z ≃1088,which has been observed in the power spectrum of CMB tem-perature anisotropy [10],temperature–polarization cross correlation [11],and distribution of galaxies [12,13].Yet,the latest observations have shown convincingly that we still do not understand much of the universe.The standard model of cosmology tells us that the universe has been dominated by four components.In chronolog-ical order the four components are:early dark energy (also known as “inflaton”fields),radiation,dark mat-ter,and late-time dark energy.The striking fact is that we do not understand the precise nature of three (dark matter,and early and late-time dark energy)out of the four components;thus,understanding the nature of these three dark components has been and will continue to be one of the most important topics in cosmology in next decades.Of which,one might be hopeful that the next generation particle accelerators such as the Large Hadron Collider (coming on-line in 2007)would find some hints for the nature of dark matter particles.On the other hand,the nature of late-time dark energy,which was dis-covered by measurements of luminosity distance out to distant Type Ia supernovae [14,15],is a complete mys-tery,and many people have been trying to find a way to constrain properties of dark energy (see,e.g.,[16]for a review).How about the early dark energy,inflaton fields,which caused the expansion of the universe to accelerate in the very early universe?We know little about the nature of inflaton,just like we know little about the nature of late-time dark energy.The required property of infla-ton fields is basically the same as that of the late-time2dark energy component:both must have a large negativepressure which is less than−1/3of their energy density. To proceed further,however,one needs more informationfrom observations.Different inflation models make spe-cific predictions for the shape of the power spectrum[8](see also Appendix B)as well as for other statistical prop-erties[17]of primordial perturbations.Therefore,one ofthe most promising ways to constrain the physics of in-flation,hence the nature of early dark energy in the uni-verse,is to determine the shape of the primordial power spectrum accurately from observations.For example,theCMB data from the Wilkinson Microwave Anisotropy Probe[1],combined with the large-scale structure datafrom the Two-Degree Field Galaxy Redshift Survey[18], have already ruled out one of the popular inflationarymodels driven by a self-interacting massless scalarfield [19].Understanding the physics of inflation better willlikely provide an important implication for late-time dark energy.“Radiation”in the universe at around the matter-radiation equality mainly consists of photons and neu-trinos;however,neutrinos actually stop being radiationwhen their mean energy per particle roughly equals the temperature of the universe.The physics of neutrinoshas been revolutionized over the last decade by solar, atmospheric,reactor,and accelerator neutrino experi-ments having provided strong evidence forfinite neutrino masses via mixing between different neutrinoflavors,theso-called neutrino oscillations[20,21,22,23,24].These experiments are,however,only sensitive to mass squaredifferences between neutrino mass eigenstates,implying ∆m221≃7×10−5eV2and∆m232≃3×10−3eV2;thus, the most fundamental quantity of neutrinos,the abso-lute mass,has not been determined yet.Cosmologicalneutrinos that are the relic of the cosmic thermal his-tory have distinct influences on the structure formation.Their large energy density,comparable to the energy den-sity of photons before the matter-radiation equality,de-termines the expansion history of the universe.Even after the matter-radiation equality,neutrinos having be-come non-relativistic affect the structure formation by suppressing the growth of matter densityfluctuations at small spatial scales owing to their large velocity disper-sion[25,26,27,28,29,30](see Sec.II and Appendix A for more details).Therefore,the galaxy redshift surveys, combined with the CMB data,provide a powerful,albeit indirect,means to constraining the neutrino properties [31,32,33,34,35].This approach also complements the theoretical and direct experimental efforts for under-standing the neutrino physics.In fact,the cosmological constraints have placed the most stringent upper bound on the total neutrino mass,mν,tot<∼0.6eV(2σ)[36], stronger than the direct experiment limit<∼2eV[37].In addition,the result obtained from the Liquid Scintillator Neutrino Detector(LSND)experiment,which implies¯νµto¯νe oscillations with∆m2>∼0.2eV2[38]in an apparent contradiction with the other neutrino oscillation experi-ments mentioned above,potentially suggests the need for new physics:the cosmological observations will provide independent tests of this hypothesis.In this paper we shall study the capability of future galaxy surveys at high redshifts,combined with the CMB data,for constraining(1)the neutrino properties,more specifically the total neutrino mass,mν,tot,and the num-ber of non-relativistic neutrino species,N nrν,and(2)the shape of the primordial power spectrum that is parame-terized in terms of the spectral tilt,n s,and the running index,αs,motivated by inflationary predictions(see Ap-pendix B).For the former,we shall pay particular at-tention to our ability to simultaneously constrain mν,tot and N nrν,as they will provide important clues to resolv-ing the absolute mass scale as well as the neutrino mass hierarchy.The accuracy of determining the neutrino pa-rameters and the power spectrum shape parameters will be derived using the Fisher information matrix formal-ism,including marginalization over the other cosmologi-cal parameters as well as the galaxy bias.Our analysis differs from the previous work on the neutrino parameters in that we fully take into account the two-dimensional nature of the galaxy power spec-trum in the line-of-sight and transverse directions,while the previous work used only spherically averaged,one-dimensional power spectra.The geometrical distortion due to cosmology and the redshift space distortion due to the peculiar velocityfield will cause anisotropic features in the galaxy power spectrum.These features help to lift degeneracies between cosmological parameters,sub-stantially reducing the uncertainties in the parameter de-terminations.This is especially true when variations in parameters of interest cause modifications in the power spectrum shape,which is indeed the case for the neutrino parameters,tilt and running index.The usefulness of the two-dimensional power spectrum,especially for high-redshift galaxy surveys,has been carefully investigated in the context of the prospected constraints on late-time dark energy properties[39,40,41,42,43,44,45].We shall show the parameter forecasts for future wide-field galaxy surveys that are already being planned or seriously under consideration:the Fiber Multiple Object Spectrograph(FMOS)on Subaru telescope[46],its sig-nificantly expanded version,WFMOS[47],the Hobby–Ebery Telescope Dark Energy eXperiment(HETDEX) [48],and the Cosmic Inflation Probe(CIP)mission[49]. To model these surveys,we consider three hypothetical galaxy surveys which probe the universe over different ranges of redshift,(1)0.5≤z≤2,(2)2≤z≤4and (3)3.5≤z≤6.5.Wefix the sky coverage of each sur-vey atΩs=300deg2in order to make a fair compari-son between different survey designs.As we shall show below,high-redshift surveys are extremely powerful for precision cosmology because they allow us to probe the linear power spectrum down to smaller length scales than surveys at low redshifts,protecting the cosmological in-formation against systematics due to non-linear pertur-bations.We shall also study how the parameter uncertainties3 are affected by changes in the number density of sam-pled galaxies and the survey volume.The results wouldgive us a good guidance to defining the optimal surveydesign to achieve the desired accuracies in parameter de-terminations.The structure of this paper is as follows.In Sec.II,wereview the physical pictures as to how the non-relativistic(massive)neutrinos lead to scale-dependent modifica-tions in the growth of mass clustering relative to thepure CDM model.Sec.III defines the parameterization of the primordial power spectrum motivated by inflation-ary predictions.In Sec.IV we describe a methodology to model the galaxy power spectrum observable from aredshift survey that includes the two-dimensional nature in the line-of-sight and transverse directions.We thenpresent the Fisher information matrix formalism that is used to estimate the projected uncertainties in the cos-mological parameter determination from statistical errors on the galaxy power spectrum measurement for a givensurvey.After survey parameters are defined in Sec.V, we show the parameter forecasts in Sec.VI.Finally,wepresent conclusions and some discussions in Sec.VII.We review the basic properties of cosmological neutrinos inAppendix A,the basic predictions from inflationary mod-els for the shape of the primordial power spectrum in Ap-pendix B,and the relation between the primordial powerspectrum and the observed power spectrum of matter densityfluctuations in Appendix C.In the following,we assume an adiabatic,cold dark matter(CDM)dominated cosmological model withflatgeometry,which is supported by the WMAP results [1,36],and employ the the notation used in[51,52]:the present-day density of CDM,baryons,and non-relativistic neutrinos,in units of the critical density,aredenoted asΩc,Ωb,andΩν,respectively.The total mat-ter density is thenΩm=Ωc+Ωb+Ων,and fνis theratio of the massive neutrino density contribution toΩm: fν=Ων/Ωm.II.NEUTRINO EFFECT ON STRUCTUREFORMATIONThroughout this paper we assume the standard ther-mal history in the early universe:there are three neutrinospecies with temperature equal to(4/11)1/3of the photon temperature.We then assume that0≤N nrν≤3species are massive and could become non-relativistic by thepresent epoch,and those non-relativistic neutrinos have equal masses,mν.As we show in Appendix A,the den-sity parameter of the non-relativistic neutrinos is given byΩνh2=N nrνmν/(94.1eV),where we have assumed 2.725K for the CMB temperature today[50],and h is the Hubble parameter defined as H0=100h km s−1Mpc−1. The neutrino mass fraction is thus given byfν≡Ων0.658eV 0.141eVΩm h21+z 1/2.(2)Therefore,non-relativistic neutrinos with lighter masses suppress the growth of structure formation on larger spa-tial scales at a given redshift,and the free-streaming length becomes shorter at a lower redshift as neutrino velocity decreases with redshift.The most important property of the free-streaming scale is that it depends on the mass of each species,mν,rather than the total mass,N nrνmν;thus,measurements of k fs allow us to dis-tinguish different neutrino mass hierarchy models.For-tunately,k fs appears on the scales that are accessible by galaxy surveys:k fs=0.096−0.179Mpc−1at z=6−1 for mν=1eV.On the spatial scales larger than the free-streaming length,k<k fs,neutrinos can cluster and fall into gravi-tational potential well together with CDM and baryonic matter.In this case,perturbations in all matter com-ponents(CDM,baryon and neutrinos,denoted as‘cbν’hereafter)grow at the same rate given byD cbν(k,z)∝D(z)k≪k fs(z),(3) where D(z)is the usual linear growth factor(see,e.g., Eq.(4)in[53]).On the other hand,on the scales smaller than the free-streaming length,k>k fs,perturbations in non-relativistic neutrinos are absent due to the large ve-locity dispersion.In this case,the gravitational potential well is supported only by CDM and baryonic matter,and the growth of matter perturbations is slowed down rela-tive to that on the larger scales.As a result,the matter power spectrum for k>k fs is suppressed relative to that for k<k fs.In this limit the total matter perturbations grow at the slower rate given byD cbν(k,z)∝(1−fν)[D(z)]1−p k≫k fs(z),(4) where p≡(5−√4FIG.1:Suppression in the growth rate of total matter per-turbations(CDM,baryons and non-relativistic neutrinos), D cbν(a),due to neutrino free-streaming.(a=(1+z)−1is the scale factor.)Upper panel:D cbν(a)/Dν=0(a)for the neutrino mass fraction of fν=Ων/Ωm=0.05.The number of non-relativistic neutrino species is varied from N nrν=1,2,and3 (from thick to thin lines),respectively.The solid,dashed,and dotted lines represent k=0.01,0.1,and1h Mpc−1,respec-tively.Lower panel:D cbν(a)/Dν=0(a)for a smaller neutrino mass fraction,fν=0.01.Note that the total mass of non-relativistic neutrinos isfixed to mν,tot=N nrνmν=0.66eV and0.13eV in the upper and lower panels,respectively. Eq.(2).It is thus expected that a galaxy survey with different redshift slices can be used to efficiently extract the neutrino parameters,N nrνand mν.The upper and middle panels of Figure2illustrate how free-streaming of non-relativistic neutrinos suppresses the amplitude of linear matter power spectrum,P(k), at z=4.Note that we have normalized the primordial power spectrum such that all the power spectra match at k→0(see§III).To illuminate the dependence of P(k) on mν,wefix the total mass of non-relativistic neutri-nos,N nrνmν,by fν=0.05and0.01in the upper and middle panels,respectively,and vary the number of non-relativistic neutrino species as N nrν=1,2and3.The suppression of power is clearly seen as one goes from k<k fs(z)to k>k fs(z)(see Eq.[2]for the value of k fs).The way the power is suppressed may be easily un-derstood by the dependence of k fs(z)on mν;for example,linear power spectrum at z=4due to free-streaming of non-relativistic neutrinos.Wefix the total mass of non-relativistic neutrinos by fν=Ων/Ωm=0.05,and vary the number of non-relativistic neutrino species(which have equal masses, mν)as N nrν=1(solid),2(dashed),and3(dot-dashed). The mass of individual neutrino species therefore varies as mν=0.66,0.33,and0.22eV,respectively(see Eq.[1]).The shaded regions represent the1-σmeasurement errors on P(k) in each k-bin,expected from a galaxy redshift survey observ-ing galaxies at3.5≤z≤4.5(see Table I for definition of the survey).Note that the errors are for the spherically averaged power spectrum over the shell of k in each bin.Different N nrνcould be discriminated in this case.Middle panel:Same as in the upper panel,but for a smaller neutrino mass fraction, fν=0.01.While it is not possible to discriminate between different N nrν,the overall suppression on small scales is clearly seen.Lower panel:Dependences of the shape of P(k)on the other cosmological parameters.P(k)at smaller k is more suppressed for a smaller mν,as lighter neutrinos have longer free-streaming lengths.Onvery small scales,k≫k fs(z)(k>∼1and0.1Mpc−1for fν=0.05and0.01,respectively),however,the amountof suppression becomes nearly independent of k,and de-pends only on fν(or the total neutrino mass,N nrνmν) as∆P5 ≈8fν.(5)We therefore conclude that one can extract fνand N nrνseparately from the shape of P(k),if the suppression “pattern”in different regimes of k is accurately measured from observations.5Are observations good enough?The shaded boxes in the upper and middle panels in Figure2represent the1-σmeasurement errors on P(k)expected from one of the fiducial galaxy surveys outlined in Sec.V.Wefind thatP(k)will be measured with∼1%accuracy in each k bin. If other cosmological parameters were perfectly known,the total mass of non-relativistic neutrinos as small as mν,tot=N nrνmν>∼0.001eV would be detected at more than2-σ.This limit is much smaller than the lower mass limit implied from the neutrino oscillation exper-iments,0.06eV.This estimate is,of course,unrealistic because a combination of other cosmological parameters could mimic the N nrνor fνdependence of P(k).The lower panel in Figure2illustrates how other cosmolog-ical parameters change the shape of P(k).In the fol-lowing,we shall extensively study how well future high-redshift galaxy surveys,combined with the cosmic mi-crowave background data,can determine the mass of non-relativistic neutrinos and discriminate between different N nrν,fully taking into account degeneracies between cos-mological parameters.III.SHAPE OF PRIMORDIAL POWER SPECTRUM AND INFLATIONARY MODELSInflation generally predicts that the primordial power spectrum of curvature perturbations is nearly scale-invariant.Different inflationary models make specific predictions for deviations of the primordial spectrum from a scale-invariant spectrum,and the deviation is of-ten parameterized by the“tilt”,n s,and the“running index”,αs,of the primordial power spectrum.As the pri-mordial power spectrum is nearly scale-invariant,|n s−1| and|αs|are predicted to be much less than unity. This,however,does not mean that the observed mat-ter power spectrum is also nearly scale-invariant.In Ap-pendix C,we derive the power spectrum of total matter perturbations that is normalized by the primordial cur-vature perturbation(see Eq.[C6])k3P(k,z)5H20Ωm 2×D2cbν(k,z)T2(k) k2αs ln(k/k0),(6)where k0=0.05Mpc−1,δ2R=2.95×10−9A,and A is the normalization parameter given by the WMAP collaboration[1].We adopt A=0.871,which gives δR=5.07×10−5.(In the notation of[63,64]δR=δζ.) The linear transfer function,T(k),describes the evolu-tion of the matter power spectrum during radiation era and the interaction between photons and baryons be-fore the decoupling of photons.Note that T(k)depends only on non-inflationary parameters such asΩm h2and Ωb/Ωm,and is independent of n s andαs.Also,the effects of non-relativistic neutrinos are captured in D cbν(k,z); thus,T(k)is independent of time after the decoupling epoch.We use thefitting function found in[51,52]for T(k).Note that the transfer function and the growth rate are normalized such that T(k)→1and D cbν/a→1 as k→0during the matter era.In Appendix B we describe generic predictions on n s andαs from inflationary models.For example,inflation driven by a massive,self-interacting scalarfield predicts n s=0.94−0.96andαs=(0.8−1.2)×10−3for the num-ber of e-foldings of expansion factor before the end of inflation of50.This example shows that precision deter-mination of n s andαs allows us to discriminate between candidate inflationary models(see[8]for more details). IV.MODELING GALAXY POWER SPECTRUMA.Geometrical and Redshift-Space DistortionSuppose now that we have a redshift survey of galax-ies at some redshift.Galaxies are biased tracers of the underlying gravitationalfield,and the galaxy power spec-trum measures how clustering strength of galaxies varies as a function of3-dimensional wavenumbers,k(or the inverse of3-dimensional length scales).We do not measure the length scale directly in real space;rather,we measure(1)angular positions of galax-ies on the sky,and(2)radial positions of galaxies in redshift space.To convert(1)and(2)to positions in 3-dimensional space,however,one needs to assume a ref-erence cosmological model,which might be different from the true cosmology.An incorrect mapping of observed angular and redshift positions to3-dimensional positions produces a distortion in the measured power spectrum, known as the“geometrical distortion”[54,55,56].The geometrical distortion can be described as follows.The comoving size of an object at redshift z in radial,r ,and transverse,r⊥,directions are computed from the exten-sion in redshift,∆z,and the angular size,∆θ,respec-tively,asr =∆zH(z′),(8) where H(z)is the Hubble parameter given byH2(z)=H20 Ωm(1+z)3+ΩΛ .(9)6 HereΩm+ΩΛ=1,andΩΛ≡Λ/(3H20)is the present-daydensity parameter of a cosmological constant,Λ.A trickypart is that H(z)and D A(z)in Eq.(7)depend on cosmo-logical models.It is therefore necessary to assume somefiducial cosmological model to compute the conversionfactors.In the following,quantities in thefiducial cos-mological model are distinguished by the subscript‘fid’.Then,the length scales in Fourier space in radial,kfid ,and transverse,kfid⊥,directions are estimated from theinverse of rfid and rfid⊥.Thesefiducial wavenumbers arerelated to the true wavenumbers byk⊥=D A(z)fidH(z)fidkfid .(10)Therefore,any difference between thefiducial cosmolog-ical model and the true model would cause anisotropicdistortions in the estimated power spectrum in(kfid⊥,kfid )space.In addition,shifts in z due to peculiar velocities ofgalaxies distort the shape of the power spectrum alongthe line-of-sight direction,which is known as the“redshiftspace distortion”[57].From azimuthal symmetry aroundthe line-of-sight direction,which is valid when a distant-observer approximation holds,the linear power spectrumestimated in redshift space,P s(kfid⊥,kfid ),is modeled in[39]asP s(kfid⊥,kfid )=D A(z)2fid H(z)k2⊥+k22×b21P(k,z),(11)where k=(k2⊥+k2)1/2andβ(k,z)≡−1d ln(1+z),(12)is a function characterizing the linear redshift space distortion,and b1is a scale-independent,linear biasparameter.Note thatβ(k,z)depends on both red-shift and wavenumber via the linear growth rate.Inthe infall regime,k≪k fs(z),we have b1β(k,z)≈−d ln D(z)/d ln(1+z),while in the free-streaming regime, k≫k fs(z),we have b1β(k,z)≈−(1−p)d ln D(z)/d ln(1+ z),where p is defined below Eq.(4).One might think that the geometrical and redshift-space distortion effects are somewhat degenerate in the measured power spectrum.This would be true only if the power spectrum was a simple power law.For-tunately,characteristic,non-power-law features in P(k) such as the broad peak from the matter-radiation equal-ity,scale-dependent suppression of power due to baryons and non-relativistic neutrinos,the tilt and running of the primordial power spectrum,the baryonic acoustic os-cillations,etc.,help break degeneracies quite efficiently [39,40,41,42,43,44,47,55,56].ments on Baryonic OscillationsIn this paper,we employ the linear transfer function with baryonic oscillations smoothed out(but includes non-relativistic neutrinos)[51,52].As extensively in-vestigated in[39,44,47],the baryonic oscillations can be used as a standard ruler,thereby allowing one to precisely constrain H(z)and D A(z)separately through the geo-metrical distortion effects(especially for a high-redshift survey).Therefore,our ignoring the baryonic oscillations might underestimate the true capability of redshift sur-veys for constraining cosmological parameters.We have found that the constraints on n s andαs from galaxy surveys improve by a factor of2–3when baryonic oscillations are included.This is because the baryonic os-cillations basicallyfix the values ofΩm,Ωm h2andΩb h2, lifting parameter degeneracies betweenΩm h2,Ωb h2,n s, andαs.However,we suspect that this is a rather opti-mistic forecast,as we are assuming aflat universe dom-inated by a cosmological constant.This might be a too strong prior,and relaxing our assumptions about geom-etry of the universe or the properties of dark energy will likely result in different forecasts for n s andαs.In this paper we try to separate the issues of non-flat universe and/or equation of state of dark energy from the physics of neutrinos and inflation.We do not include the bary-onic oscillations in our analysis,in order to avoid too optimistic conclusions about the constraints on the neu-trino parameters,n s,andαs.Eventually,the full analysis including non-flat uni-verse,arbitrary dark energy equation of state and its time dependence,non-relativistic neutrinos,n s,andαs, using all the information we have at hand including the baryonic oscillations,will be necessary.We leave it for a future publication(Takada and Komatsu,in prepara-tion).C.Parameter Forecast:Fisher Matrix Analysis In order to investigate how well one can constrain the cosmological parameters for a given redshift survey de-sign,one needs to specify measurement uncertainties of the galaxy power spectrum.When non-linearity is weak, it is reasonable to assume that observed density perturba-tions obey Gaussian statistics.In this case,there are two sources of statistical errors on a power spectrum measure-ment:the sampling variance(due to the limited number of independent wavenumbers sampled from afinite sur-vey volume)and the shot noise(due to the imperfect sampling offluctuations by thefinite number of galax-ies).To be more specific,the statistical error is given in [58,59]by∆P s(k i)N k 1+1。

聚酰亚胺文献

聚酰亚胺文献

M
structure between the ammonium cation of Lys-108 and the four π-electron-rich aromatic walls of Trp-120, Trp-52, Tyr-50, and Tyr-116.5 Inspired by the biological recognition motifs for the charged ammonium substrates,6 the design and development of artificial ammonium receptors represent a fascinating area of research in supramolecular chemistry. Consequently, a particular attention has been devoted to the recognition of ammonium guests by macrocycles such as calixarenes,7 pillarenes,8 crown ethers,9 and cucurbiturils.10 Regarding the calixarene macrocycles, Pappalardo and Parisi reported the first examples in which a preformed 20-membered calix[5]arene cavity 1a (Chart 1) was exploited for the endocavity complexation of linear alkylammonium guests.7b−d Successively, we have obtained the first examples of endo-cavity complexation of large calix[6,7]arene macrocycles7g,h 1b,c (24Chart 1

THE MASS SPECTROMETER

THE MASS SPECTROMETER

THE MASS SPECTROMETERHow a mass spectrometer worksThe basic principleIf something is moving and you subject it to a sideways force, instead of moving in a straight line, it will move in a curve - deflected out of its original path by the sideways force.Suppose you had a cannonball travelling past you and you wanted to deflect it as it went by you. All you've got is a jet of water from a hose-pipe that you can squirt at it. Frankly, its not going to make a lot of difference! Because the cannonball is so heavy, it will hardly be deflected at all from its original course.But suppose instead, you tried to deflect a table tennis ball travelling at the same speed as the cannonball using the same jet of water. Because this ball is so light, you will get a huge deflection.The amount of deflection you will get for a given sideways force depends on the mass of the ball. If you knew the speed of the ball and the size of the force, you could calculate the mass of the ball if you knew what sort of curved path it was deflected through. The less the deflection, the heavier the ball.An outline of what happens in a mass spectrometerAtoms can be deflected by magnetic fields - provided the atom is first turned into an ion. Electrically charged particles are affected by a magnetic field although electrically neutral ones aren't.The sequence is :Stage 1: IonisationThe atom is ionised by knocking one or more electrons off to give a positive ion. This is true even for things which you would normally expect to form negative ions (chlorine, for example) or never form ions at all (argon, for example). Mass spectrometers always work with positive ions.Stage 2: AccelerationThe ions are accelerated so that they all have the same kinetic energy.Stage 3: DeflectionThe ions are then deflected by a magnetic field according to their masses. The lighter they are, the more they are deflected.The amount of deflection also depends on the number of positive charges on the ion - in other words, on how many electrons were knocked off in the first stage. The more the ion is charged, the more it gets deflected.Stage 4: DetectionThe beam of ions passing through the machine is detected electrically.A full diagram of a mass spectrometerUnderstanding what's going onThe need for a vacuumIt's important that the ions produced in the ionisation chamber have a free run through the machine without hitting air molecules.IonisationThe vaporised sample passes into the ionisation chamber. The electrically heated metal coil gives off electrons which are attracted to the electron trap which is a positively charged plate.The particles in the sample (atoms or molecules) are therefore bombarded with a stream of electrons, and some of the collisions are energetic enough to knock one or more electrons out of the sample particles to make positive ions.Most of the positive ions formed will carry a charge of +1 because it is much more difficult to remove further electrons from an already positive ion.These positive ions are persuaded out into the rest of the machine by the ion repeller which is another metal plate carrying a slight positive charge.AccelerationThe positive ions are repelled away from the very positive ionisation chamber and pass through three slits, the final one of which is at 0 volts. The middle slit carries some intermediate voltage. All the ions are accelerated into a finely focused beam.DeflectionDifferent ions are deflected by the magnetic field by different amounts. The amount of deflection depends on:∙the mass of the ion. Lighter ions are deflected more than heavier ones.∙the charge on the ion. Ions with 2 (or more) positive charges are deflected more than ones with only 1 positive charge.These two factors are combined into the mass/charge ratio. Mass/charge ratio is given the symbol m/z (or sometimes m/e).For example, if an ion had a mass of 28 and a charge of 1+, its mass/charge ratio would be 28. An ion with a mass of 56 and a charge of 2+ would also have a mass/charge ratio of 28.In the last diagram, ion stream A is most deflected - it will contain ions with the smallest mass/charge ratio. Ion stream C is the least deflected - it contains ions with the greatest mass/charge ratio.It makes it simpler to talk about this if we assume that the charge on all the ions is 1+. Most of the ions passing through the mass spectrometer will have a charge of 1+, so that the mass/charge ratio will be the same as the mass of the ion.Assuming 1+ ions, stream A has the lightest ions, stream B the next lightest and stream C the heaviest. Lighter ions are going to be more deflected than heavy ones.DetectionOnly ion stream B makes it right through the machine to the ion detector. The other ions collide with the walls where they will pick up electrons and be neutralised. Eventually, they get removed from the mass spectrometer by the vacuum pump.When an ion hits the metal box, its charge is neutralised by an electron jumping from the metal on to the ion (right hand diagram). That leaves a space amongst the electrons in the metal, and the electrons in the wire shuffle along to fill it.A flow of electrons in the wire is detected as an electric current which can be amplified and recorded. The more ions arriving, the greater the current.Detecting the other ionsHow might the other ions be detected - those in streams A and C which have been lost in the machine?Remember that stream A was most deflected - it has the smallest value of m/z (the lightest ions if the charge is 1+). To bring them on to the detector, you would need to deflect them less - by using a smaller magnetic field (a smaller sideways force).To bring those with a larger m/z value (the heavier ions if the charge is +1) on to the detector you would have to deflect them more by using a larger magnetic field.If you vary the magnetic field, you can bring each ion stream in turn on to the detector to produce a current which is proportional to the number of ions arriving. The mass of each ion being detected is related to the size of the magnetic field used to bring it on to the detector. The machine can be calibrated to record current (which is a measure of the number of ions) against m/z directly. The mass is measured on the 12C scale.THE MASS SPECTRA OF ELEMENTSThe mass spectrum for boronThe mass spectrum for zirconiumThe number of peaks in the mass spectrum shows the number of the isotopes for an element.The total mass of these 100 typical atoms would be(51.5 x 90) + (11.2 x 91) + (17.1 x 92) + (17.4 x 94) + (2.8 x 96) = 9131.8The average mass of these 100 atoms would be 9131.8 / 100 = 91.3 (to 3 significant figures).91.3 is the relative atomic mass of zirconium.Note: When you calculate the relative atomic mass for element, the total of % of abundance is 100%.。

Mass Spectrometry

Mass Spectrometry
For ex. GC-MS, LC-MS, MS-MS, or CE-MS GCLCMSCE-
Advantages of MS
1.
2.
Detection limits up to 3 orders of magnitude better than optical methods Remarkably simple spectra that are usually unique and easily interpretable
Direct Probe Inlet
Good for solid and nonnon-volatile liquids Sample is on surface, probe positioned near ionization source and slit leading to spectrometer Good for low concentrations or thermally unstable compounds
TONS of applications!
Regiospecific Analysis of Diricinoleoylacylglycerols in Castor (Ricinus communis L.) Oil by Electrospray IonizationIonization-Mass Spectrometry Characterization of Puff-by-Puff Resolved Cigarette Puff-byMainstream Smoke by Single Photon Ionization-TimeIonization-Timeof-Flight Mass Spectrometry and Principal Component ofAnalysis Electrospray Ionization Mass Spectrometry Fingerprinting of Brazilian Artisan Cachaça Aged in Different Wood Casks Determination of Nitrofuran Residues in Milk of Dairy Cows Using Liquid Chromatography-Tandem Mass ChromatographySpectrometry

固相萃取—气相色谱—质谱法同时测定甜瓜中11种有机磷农药残留量

固相萃取—气相色谱—质谱法同时测定甜瓜中11种有机磷农药残留量

2019,32(8):124-128中国瓜菜试验研究固相萃取一气相色谱一质谱法同时测定甜瓜中11种有机磷农药残留量乌卩阳I,郭艳琼舄王建军蔦耶杰蔦付峰',何建东蔦翟泰宇蔦蔺玉珍2(1.包头市农产品质量安全检验检测中心内蒙古包头014010;2.包头市农畜产品质量安全监督管理中心内蒙古包头014010)摘要:为了建立固相萃取(SPE)气相色谱-质谱法(GC-MS),同时测定甜瓜中11种有机磷农药含量的分析方法,甜瓜样品釆用乙睛提取,经Cleanert PC/NH2固相萃取小柱净化,GC-MS分析,选择离子监测模式,外标法定量。

结果表明,11种有机磷农药在质量浓度0.05-2.00mg•L"线性关系良好(/>0.99),定量限在0.01-0.20mg-kg'之间。

3个添加水平下,11种有机磷农药的平均回收率为82.2%~103.4%,相对标准偏差(RSD)为1.1%~11.2%O该方法前处理简便,准确度、精密度和灵敏性都符合农药多残留检测的要求,结果令人满意。

关键词:甜瓜;有机磷农药;残留量;固相萃取;气相色谱-质谱Simultaneous determination of11organophosphorus pesticide residues in muskmelon by GC-MS with solid-phase extractionWUYang1,GUO Yanqiong',WANG Jianjun',WU Jie1,FU Feng1,HE Jiandong',ZHAI Taiyu2,LIN Yuzhen2 {1.Center f or Detection and Inspection of A gricultural Products Quality and Safety of B aotou,Baotou014010,Inner Mongolia,China;2.Baotou Liverstock Products Quality and Security Supervisin and Management Center,Baotou014010,Inner Mongolia,China)Abstract:To establish a method for the determination of11organophosphorus pesticide residues in muskmelon using solid-phase extraction(SPE)and gas chromatography-mass spectrometry(GC-MS).The pesticides were extracted with acetonitrile,and cleaned up on a Cleanert PC/NH2SPE column,The analytes were determined by GC-MS,selective ion monitoring(SIM)model,external standard method were used for the quantification.The results showed that the linearity range of the method between0.05-2.00mg•L1was satisfying and the limit of quantitation(LOQ)of all pesticides were0.01-0.20mg•kgThe results of the spiked level test showed that the average recovery of11organophospho­rus pesticides ranged from82.2%-103.4%with relative standard deviations(RSDs)of1.1%-11.2%at the3spike levels.The pretreatment of the method was simple,the accruracy,precision and sensitivity of the method can meet the require­ments of the multiple pesticide residue analysis,and the result was satisfactory.Key words:Muskmelon;Organophosphorus pesticide;Residues;Solid-phase extraction;GC-MS有机磷农药是我国使用广泛、用量最大的杀虫剂。

质谱(massspectrum)

质谱(massspectrum)

质谱(mass spectrum)Mass spectrometry (MS), 2010-05-22, 22:597.4.1 principleMass spectrometry is one of the important methods to determine the structure of organic compounds developed in the 40s of this century. The mass spectrometer mainly consists of four partsIonization variable arc magnetic field ion collector recorderIn mass spectrometry, the sample is converted to vapor in the ionization chamber. The ionization chamber is a high vacuum (10-8 mmHg), an electron source in the ionization chamber, the electron beam can emit high energy, organic compounds by high-energy electron beam bombardment, they can lose an outer electrons into high molecular ions with positive charge on a.M + e, M+ + 2eThese energetic molecules can also be cleaved into a variety of positively charged cations, negatively charged anions, and uncharged fragments. There is also an accelerator in the ionization chamber, where the positive ions can be accelerated and enter the strong magnetic field below, while the negative ions and neutral fragments are not accelerated and evacuated by vacuum pumps. The magnetic field in mass spectrometry is an arc magnetic field, which enters a positive ion in a strong magnetic field. Because of their different mass of m/z, when they are moving along the arc track, m/z is differentIons vary in degrees of curvature. When the positive ion acts as an arc, the centripetal force (Hen) is balanced with thecentrifugal force mv2/R.H is the magnetic field intensity, and R is the radius of curvature of the ion motion. E, m and V are the charge, mass and velocity of ion motion, respectively.Since the ion is accelerated in an electric field whose electric field is V, its kinetic energy is equal to that of potential energy:Combine the above two formula to get:Cationic mass small, arc radius is small, and large mass cation, arc radius, so, according to the detected signal, you can know the quality of debris, that is to say, which is split into compound ions, according to these pieces, you can put the structure information for organic compounds the.7.4.2 mass spectrumThe mass spectra of m/z are in abscissa, and the ordinate is the relative abundance of ions. The maximum ion is 100% (base peak), and the maximum abundance ions are not necessarily molecular ions.Information provided by 7.4.3 mass spectrometryMass spectrometry is usually used in two ways:(a) confirm whether the two compounds are identical;(b) help determine the structure of the new compound.Mass spectrometry can determine the structure of a new compound or an unknown substance from the following aspects(1) given the correct molecular weight (molecular ion peak m/z), containing an odd number of N atomic compounds, the molecular ion peak is odd, and the rest are all even numbers.(2) according to the abundance and variety of fragments, it is possible to point out which structural units exist in the molecule.(3) according to isotopic abundance, the number of atoms such as C, Cl, Br, N and so on can be calculated.(4) given a structural formula, at least it can be reduced to very few possibilities.7.4.4 applications7.4.4.1 for element compositionBecause organic molecules contain isotopic elements, there is a M+1 peak near the molecular ion peak. According to the relative abundance of molecular ion peaks and isotopic peaks and the relative isotopic abundances of elements (Table 7.1) in mass spectra, the number of atoms in the compound can be calculated by pressing down.Table 7.1 isotopic abundance of common elements in organiccompounds element Abundance /% carbon12C 10013C 1.08 hydrogen1H 1002H 0.016 nitrogen14N 10015N 0.38 oxygen16O 10017O 0.0418O 0.20fluorine19F 100sulfur32S 10033S 0.7834S 4.40chlorine35Cl 10037Cl 32.5bromine79Br 10081Br 98iodine127I 100For example, in nature, carbon has two isotopes. The abundance of isotope 13C relative to 12C is 1.08 (100-1.08) =1.092%,therefore, the number of C atoms in organic compounds is n:N is about M+1 peak relative abundance of M / 1.1.Mass spectrometry is useful in identifying molecules containing Cl, Br, and S atoms, because these elements contain isotopes of two mass units. Thus, there is a M+2 peak in the molecular ion peak of compounds containing Cl, Br, and S. For compounds containing two Cl and Br atoms, the peaks of M+4 are often present.7.4.4.2 determines possible structures based on fragmentationWhen the molecules are dissociated, a stable cation is formed, and the more stable the ion is, the greater the peak abundance is. In addition, according to the reduction of the ion peak value, it is possible to roughly estimate the possible groups in the molecule.-CH3, M/e=15, CH3CH2-,M / E = (CH3, 2CH - 29), M / E = 43C6H5 - M / E = 77 Oh, M / E = 17Example 8 the spectrum analysis of a compound is as follows::M / Z (M +) 100%, 114, 115, 7.84%Ir:290cm 2870cm - 1, - 1 - 11700cm(six, nmr:d1.0, three); (4 d1.5, multiple peaks); (4, d2.25, three peaks)Determine the possible structure of the compound.Analysis: molecular weight 1147.84 / 1.1 = 7, with carbon atoms asO exists (1700cm, C = 1); contains 14 h atoms.The molecular formula is C7H14O, unsaturation f = 1From NMR analysis, the compound may be a symmetrical structure.The 6h atom of d1.0 may be the two - CH3, according to the three peaks, which should have the following structure: ch3ch2 -D2.25 4H atoms may be two CH2, according to the three peaks have the following structure of CH2CH2 -:-Therefore, the structure of the compound is:Ch3ch2ch2coch2ch2ch3exercises1. How many sets of absorption peaks are there in the 1HNMR spectra of the following compounds?(1) (2) pentane 2 - chloro propane(3) (4) two, three - hexamethylene glycol methyl ether(5) (6) benzyl chloride methyl 2-2 -(7) (8) vinyl chloride 1,1,4 - three butane2. According to the data of 1HNMR spectra, the structure of the following compounds is speculated:(1) C8H10, Delta h:1.2 (T, 3 points), 26 (Q, 2 hours (B), 7.1 B, wide peak], [5h] ppm(2) C10H14, Delta h:1.3 (S, 9 points), 7.3 - 7.5 (M, 5H) [M means multiple peaks), PPM(3) c6h14, Delta h:0.8 (D, 1.4, 12:00), (H, H means seven peaks) [2 points), PPM(4) c4h6cl4, Delta h:3.9 (D, 4), (T, 2 hours, 4.6) ppm(5) c4h6cl2, Delta h:2. 2 (S, 3 points), 4.1 (D, 2 h), (T, 1, 5.1) ppm(6) C8H10, Delta h:2.9 (S, (4), 7.1, B, 10) ppm3. Speculate on the structure of the following compounds:(1) M / Z:134 (M +), 119 (B), 10.5,Delta h:1.1 (T, 6:00), 2.5 (47 (Q, S), 4) ppm.(2) two, three (2 - two methyl bromide butane and CH3) 3Co + K reaction generated after two compounds: h:1.66, 8 (S); B (D, h:1.1, 8 (six), 1, 3, three. (a) H (D), 5 million 700 thousand rate of 2 hours).(3) M / Z:166 (M +), 168 (M + 2), 170 (M + 4), 131, 133, 135, 83, 85, 87, and delta h:6.0 ppm (S).(4) c6h4brno2, M / Z (M +): 201, 203 (M + 2); Delta h:7.6 (D, 2 h), 8 million 100 thousand point rate (D, 2 hours).4. 2,4,6 tritertbutyl phenol reacted with bromine in acetic acid solution, compound a (c18h29bro), generating almost quantitative yield. The infrared spectrum of a has an absorption peak at 1630 and 1650 cm - 1; there are three single peaks in the 1HNMR spectrum: delta = H = 1.19, 1.26 and 6.90ppm, with an area ratio of 9:18:2. Speculate on the structure of A.5. Speculate on the structure of the following compounds:(1) c9h12o, V max:3350307016001490, 1240, 830 - 1 cm; 8 h:0.9 (T (3) 1.5 meters, 2 hours, 2.4 (T), 2 hour (B), 5.5, one hour), 6.8 (Q 4) ppm.(2) C10H14O, in max:335016001490 years, 710 years, 690. H:1.1 cm (six - 1; 1.4 (S, S),,, (a) 2.7 S, 2 h), 7.2 (S, 5H) ppm.(3) C10H14O, V max:334016001490, 1380, 1230, 860 - 1 cm; 8 h:1.3 (B, 9 points (B points), 4.9), 7 (Q 4) ppm.(4) c9h11bro, in max:33401600 years, 15001380 years, 830 - 1cm; 8 h:0.9 (T, 3), 160 (Q, 2 hours, 2.7 (S) (T, one hour, one hour), 4.4), 7.2 (Q 4) ppm.(5) c8h18o2, V max:33501390, 1370 - 1 cm; 8 h:1.2 (S, 12:00), 150 (S, 4), (S, 2 hours) 1 million 900 thousand rate. Nonreactive with periodate.(6) in max:36001600 years, 15001160 years, 1010, 690760 - 1 cm; (S, h:2.8, 8 hours), 7.3 (S, 15h) ppm, MS, M / Z:260183, 78.(7) in max:360030301600 years, 1500826 years - 1180, 1020 cm, 1; 8 h:5.1 (S, a D2O, disappeared after) 6.8 (Q 4) ppm, MS, M / Z:176 (M + 4), 174 (M (M + 2), + 172, B). 93 (19.5), 75 (1), 65 (31).(8) V max:3200 1500 (B), (B), 1480, 1200820 - 1 cm; 8 h:7.5 (S, 2 hours after the addition of D2O, S 6.6 (gone),4h) ppm; ms, m / z: 110 (m + b).(9) c12h18o2, δh: 1.2 (h, 6h), 3.4 (q, 4h), 4.4 (s, 4h), 7.2 (s, 4h) ppm; 用高锰酸钾氧化生成对苯二甲酸.(10) c6h14o, δh: 1.2 (d, 12h), 3.6 m, 2h), ppm.(11) c14h14o, δh: 4.5 (s, 4h), 7.3 (s, 10h) ppm; νmax: 3070, 1100 cm - 1.(12) c9h10o, νmax: 3070, 1500, 1120, 750 cm - 1; δh: 2.8 (t, 2h), 3.9 (t, 2h), 4.7 (s, 2h), 7.1 (m, 4h) ppm. (提示: 此化合物为邻位二取代苯)(13) c8h10o, νmax: 1600, 1500, 1380, 1260, 1030, 810 cm - 1; δh: 2.3 (s, 3h) 3.8 (s, 3h), 7.0 (q, 4h) ppm.(14) c8h10o, νmax: 1600, 1500, 1260, 1040 cm - 1; δh: 1.3 (t, 3h), 3.9 (q, 2h), 7.0 (m, 5h) ppm.6. 下列化合物的核磁共振谱中只有一个单峰. 试写出它们的结构式:(1) c2h6o (2) c4h6 (3) c4h8(4): c5h12 (5) c2h4cl2 (6) c8h187. 化合物a的相对分子质量为100, 与nabh4作用后得到b. b的相对分子质量为102. b的蒸汽于高温通过氧化铝得到c. c的相对分子质量为84. c经臭氧化分解后得到d和e. d能发生碘仿反应而e不能. 试根据以上化学反应和a的如下图谱数据, 推测a的结构, 并写出各步反应式.a的ir (cm - 1): 1712, 1383, 1376a的nmr: delta (ppm) 1.00 1.13 2.13 3.52峰型三双四多峰面积 7.1 13.9 4.5 2.3核磁共振谱 (nmr) 2010 - 05 - 22 22: 59红外光谱和核磁共振是有机化学研究领域应用最广泛的两种不可缺少的分析手段.核磁共振谱的研究对象是有机化合物中的h原子.对于一个化合物, 经红外光谱测定后, 能够清楚, 这个化合物属于什么类型的化合物, 而核磁共振测定, 则可以给出这是一个什么具体的化合物, 让我们先看一看一张真正的核磁共振谱图, 对结构测定所起的作用:从一张nmr, 可得到如下信息:1、信号的数目: 提供分子中质子类型信息2、信号的位置: 提供质子的电子环境信息3、信号的强度: 提供质子的个数4、信号分裂情况: 提供这个质子周围相邻质子的种类及个数的信息.为什么核磁共振能提供这么多的结构信息? 为了解决这个问题, 我们还是先看一看, 核磁共振是怎么回事.10 9 8 7 6 5 4 3 2 1 0 d / ppm溴乙烷的1hnmr7.3.1 核磁共振现象氢原子核带有一个质子, 象电子一样, 原子核也是自旋的.质子自旋也有两种取向: + 1 / 2和 - 1 / 2, 在通常情况下, 质子两个自旋态的能量相等.质子自旋时, 可产生一个磁场, 两种取向的质子会产生两种不同取向的磁矩.如果把质子放到外加磁场h0中, 两种取向质子产生的磁矩有一种与外磁场同向, 另一种将与外磁场反向.质子的两种取向在外磁场下能量不同.与外磁场同的取向能量较低, 两个能级之差为Δe、Δe与外磁场强度h0成正比:r为核常数, 称为磁旋比, h为普朗克常数.若质子受到一定频率的电磁波辐射, 当辐射所提供的能量恰好等于质子两种取向的能级差Δe时, 质子就会吸收电磁辐射的能量, 从低能级跃迁到高能级, 这种现象叫核磁共振.核磁共振现象, 在其它原子序数为单数的原子核中也存在, 例13c、19f (都有成单的核电荷).在有机分子中, 一般都是12c、16o、12s 等, 这些原子都不存在核磁共振现象.近年来, 13cnmr发展很快.从理论上讲,The matter can be put in a constant intensity magnetic field, and an NMR spectrum is obtained by the same method as the infrared spectrum. That is, gradually change the frequency of radiation, and then observe the absorption of the material radiation frequency, but in practical applications, the better way is to keep the radiation frequency constant, and change the intensity of the magnetic field. Proton orientation energyThe difference between the radiation and the radiation is matched, i.e., the radiation absorption is satisfied under the lower formProtons can produce absorption, and a signal can be observed.According to this analysis, all protons in an organic molecule are low in the field and high in the fieldBoth will be absorbed at exactly the same magnetic field intensity, so the spectrum of the magnetic field is scannedThere will be only one signal, but why is there a different signal in the NMR?7.3.2 degrees DeltaFormation of 7.3.2.1 chemical shift DeltaThe case discussed above is the spin of protons, protons in the organic compounds, and electrons around them, while the different types of H atoms have different densities of the surrounding electron clouds. In the applied magnetic field, the electron cloud forms an electron circulation. The formation of another magnetic field in the circulation, that is, the induced magnetic field, the direction of the induced magnetic field, and the external magnetic field in reverse direction. The induced magnetic field produced by the electron circulation around the proton must counteract the strength of a part of the external magnetic field. Thus, the magnetic field that the proton feels is lower than the strength of the external magnetic field. Typically less than a few millionth of a fraction, that is, ppm, we say that protons are shielded.So, in the electron cloud density of protons around the greater shielding effect is larger in the proton magnetic field strength will be higher under resonance, therefore, for different proton electronic environment, outer magnetic resonance need different, this is because they have different shielding effect, we have different resonance the strength ofthe magnetic field due to the shielding effect is different by proton chemical shift. As a result, signals in different positions appear in NMR, so that the magnitude of the chemical shift reflects the electronic environment around the proton directly.Representation of 7.3.2.2 chemical shiftsHow do we measure and represent the magnitude and orientation of a chemical shift? The intensity of the induced magnetic field is proportional to the applied magnetic field strength H0, that is, the chemical shift is also dependent on the applied magnetic field strength, and the unit of chemical shift can be expressed in Hz (frequency units). In practice, the standard substance used is 4Si (CH3). Because of the shielding effect of protons in (CH3) 4Si, protons are larger than protons in most organic compounds. If a small amount of TMS is added to the other sample, all protons in the sample will appear on the left of the TMS signal. After the nuclear magnetic resonance instrument is debugged, the signal of the TMS can fall on the zero line of the chart recording paper. The proton signal in the sample is low in the TMS field, and the chemical shift of the proton to be measured (Hz) can be directly read out.The intensity of the induced magnetic field is related to the applied magnetic field strength H0. Therefore, when using Hz to indicate the chemical shift, the frequency of the NMR must be explained. The commonly used MRI devices are 60, 90, 100, 220, 450, MHz.If the observed shift is divided by the frequency used by theinstrument, then the chemical shift is a constant, independent of the operating conditions (H0 and radio frequency) of the NMR instrument.Under the above definition, the delta of TMS is 0, and the magnitude of delta increases gradually from right to left in the NMR spectrum, opposite to the order of the sweep field (delta =0, corresponding to the high field).The chemical shift value, like the absorption frequency of infrared spectrum, is an important physical constant of organic compounds. The chemical shifts of protons of different types are shown in the following table.Proton typechemical shiftProton typechemical shiftH - C - R0.9 - 1.8H - C - NR2.2 - 2.9H - C - C=C1.6 -2.6H - C - Cl3.1 -4.1H - C - C=O2.1 - 2.5H - C - Br2.7 - 4.1H - CoC-Two point fiveH - C - O3.3 - 3.7H - C - Ar2.3 - 2.8H - NR1 - 3H - C=C-4.5 - 6.5H - OR0.5 - 5H - Ar6.5 - 8.5H - OAr6 - 8H - C=O9 - 10H - O - C=O10 - 13Variation law of delta values in 7.3.2.3 organic compoundsThe greater the electron density around the proton, the greater the induced magnetic field, the greater the external magnetic field required for the proton transition, i.e., the smaller the delta at the high field. According to this analysis, the delta value varies as follows:(1) delta values increase sequentially from R-CH3, R2CH2, and R3C-H.(R even on saturated carbon atoms, -I effect)(2) the delta value increases with the increase of electronegativity of neighboring atoms(3) the delta value decreases with the increase of the distance between the H atom and the electronegative group(4) delta values increase from alkyl, alkenyl, and aryl groups:Delta value: R - C - H, < =C - H, Ar - HBut the delta value of CoC - H is small =C-H, and the value of H Delta on aryl is especially large.In C=C, CoC, and PhH, the direction of the induced magnetic field in PI is as follows:The H atom on the double bond and benzene is falling in the same direction as the direction of the applied magnetic field in the direction of the induced magnetic field, so that the shielding effect of the proton decreases and the delta value increases, which is called the shielding effect of H0. But different H atoms in the alkyne alkyne, falls on the induction magnetic field and external magnetic field in the opposite direction, increase the shielding effect by proton, delta value decreased, therefore, the H value is smaller than the acetylene ethyleneDelta, with some alkanes almost.According to the size of the diamagnetic circulation, it is possible to determine whether a closed ring is aromatic.[18] eneBecause of the shielding effect, the outer proton is very large (delta =8.2ppm). The proton in the ring is very shielded and the delta is negative (delta =-1.99ppm).The intensity and number of peaks in 7.3.3 NMR spectraThe number of 7.3.3.1 peaks represents the chemically equivalent proton species (hydrogen atom species)Protons with different chemical shifts are called chemically equivalent protons. Each chemical is not equivalent, and the proton has a different delta value in the NMR spectrum. The judgment of two proton is chemical equivalent they are using the same atom substituted Z respectively, such as two protons are replaced by the same structure, or enantiomers, which is equivalent to two proton proton chemical shifts of the same chemical.CH3CH3: 6 H are chemically equivalent protonsCl HaC, C, Ha and Hb are chemically non equivalent protonsBr HbHa and Hb are chemically non equivalent protonsHa and Hb are chemically equivalent protons.The ratio of the 7.3.3.2 peak area represents the proton number ratioAll NMR spectra are like this: the peak area is directly proportional to the number of protons. In a standard spectrum, it is not written directly how many protons each signal has, but instead is represented by a ladder curve.This curve is drawn from the electronic integral in the instrument, which reflects the number of protons. Integral curve drawing is from low to high field field (left to right), the total height of the integral curve starting point to the end point (area) the number of all hydrogen atoms and molecules is proportional to a single step in each of these steps under the above signal, the ratio of height (area) is the number of H atoms produced a variety of signal ratio.The NMR spectra are painted on the grid paper, so the count under the curve number, it is easy to determine the number of H atoms.Splitting and spin coupling of 7.3.4 peaks7.3.4.1 splitting and couplingIn an actual NMR, each signal is not a single peak, but splitsinto several peaks. In NMR, the phenomenon of splitting signals into several peaks is called splitting of peaks.The splitting phenomenon is caused by spin coupling (spin interference) between protons on two adjacent carbon atoms. As already mentioned, the proton is the spin, each small proton is equivalent to a small magnet, if two protons are very close (in words on adjacent carbon atoms), one proton affected by another proton magnetic fields generated by the. The magnetic field that is felt at a certain moment has a slight increase and decrease. That is to say, the proton to the actual experience at that time the field strength is not H0, but sometimes slightly more than H0, sometimes slightly less than H0, therefore, the signal is split into two peaks, in order to better understand this phenomenon, please look at the following example.First look at the two Hb protons, the B proton has only one a proton near it, and a spins in the outer magnetic field in two cases:+1/2H0- 1/2Or parallel to an external magnetic field, or opposite to an external magnetic field. If the spin of the a proton is parallel to the external magnetic field at a certain moment, the magnetic field experienced by the B proton is greater than H0, and ifthe spin of the a proton reverses the diamagnetic field, the magnetic field that the B protons experience is less than H0. As a result, the B protons split into double peaks under the combined action of the neighboring a protons and the external magnetic field H0,One moves toward the low field, one moves toward the high field, because the a proton has the same probability of the two kinds of spin, so the strength of the B proton double peak is equal.Now consider the spin coupling of 2 B protons to the a proton.The spin of the two B protons is more complicated than the spin of the 1 a protons.+10 H02 B protons - 1There are 4 sets of spin directions with equal likelihood, in which the two groups are the same, so that at any time the a protons feel one of the three magnetic fields, and its signal splits into three peaks, with a relative strength of 1:2:1. The total spin quantum number is 0 of the combination, the peak position in the middle, the remaining two, one at the high field, one at the low field. Since they produce the same magnetic field, they are only in opposite directions, so the distance between them is equal. The distance between the two peaks is called the coupling constant, expressed in J, and the unit is Hz.7.3.4.2 splitting law(1) when the spin coupling of N neighboring H atoms is simultaneous, the splitting fraction is n+1, and the intensity of the peak conforms to the (a+b) n expansion coefficient relationship.N=1 11N=2 121N=3 1331N=4 14641(2) when the spin coupling of the neighboring H atoms is not simultaneous, the number of splittings is (n+1) (n, +1) (n '+1')... In the case of (1+1) (1+1), the peaks are four peaks. For example, in Cl2CHCH2CHBr2, CH2 splits into four peaks, and the intensities of peaks are equal. For other cases, the splitting of peaks can not be resolved, and they are collectively referred to as multiple peaks.(3) the same H atoms do not couple, for example, the H atoms in -CH3 do not couple with each other, and the H atoms in CH3-CH3 do not couple.7.3.4.3 coupling constantThe distance between two adjacent peaks in a multiple peak iscalled the coupling constant, expressed in J. The unit is Hz, and the coupling constant is a useful amount, which indicates the intensity of the interference between the two protons. The greater the interference, the greater the coupling constant. Thus, the coupling constant often gives the exact information needed to find the molecular structure, and for a beginner, know the following points:(1) the two kinds of protons that interfere with each other, their coupling constant must be equal, for example: CH3CHCl2Jab=JbaCH2 -CH3(2) the size of the coupling constant is determined by the phase coupling structure of the proton.Jab= 2~15 HzJbc= 0~7 HZJac= 10~21 HZHC, C, J = 2~13C - HH HHJ=2~6HZ J=5~14HZHDistinguishable conformational isomers(3) the two groups of peaks that are mutually coupled are gradually ascending upward from the outermost peak.- CH - CH2-4, the limit of spin coupling(1) the so-called neighboring H atoms usually refer to H on the same carbon or ortho carbon. The spin interaction disappears as the distance increases.(2) the effect of heavy bonds is greater than that of single bonds.(3) the -OH in H is not normally coupled with neighboring protons, such as CH3OH, for single peaks. If the H exchange rate of -OH is slowed by DMSO with extremely pure alcohols and solvents, the CH3 has double bonds, and the OH on the H has four peaks。

仪器分析—质谱11

仪器分析—质谱11
• Direct insertion probe
• Conceptually very easy, practically very tricky
Sample
Ceramic tip V acuum s e a ls
21
Sample Introduction: Gas Chromatography-MS (GC-
-Formation of ions in the gas phase (many ways)
• positive ion: by adding a proton: (M+H) + • or by removing an electron: (M ) +
• negative ion: by removing a proton: (M-H) • or by adding an electron: (M) -
6
质谱法的主要作用是:
(1)准确测定物质的分子量
(2)根据碎片特征进行化合物的结构分析 分析时,首先将分子离子化,然后利用离 子在电场或磁场中运动的性质,把离子按 质核比大小排列成谱——质谱。
7
HOW DO WE ACHIEVE THIS?
• PERSUADE THE MOLECULE TO ENTER THE VAPOR PHASE (CAN BE DIFFICULT) • PRODUCE IONS FROM THE MOLECULES THAT ENTER THE GAS PHASE • SEPARATE THE IONS ACCORDING TO THEIR
Environmental analysis
Pesticides on foods, soil and groundwater contamination

微波等离子体飞行时间质谱仪研制及元素检测应用研究

微波等离子体飞行时间质谱仪研制及元素检测应用研究

LOS A, MAKAROV A. Fourier transform mass spec-trometry[J]. Molecular & Cellular Proteomics, 2011,10(7): 1-19.PAINTER T A, MARKIEWICZ W D, MILLER J R,BOLE S T, DIXON I R, CANTRELL K R, KENNEY S J, TROWELL A J, KIM D L, LEE B S, CHOI Y S, KIM H S, HENDRICKSON C L, MARSHALL A G. Require-ments and conceptual superconducting magnet design for a 21 T Fourier transform ion cyclotron resonance mass spectrometer[J]. IEEE Transactions on Applied Super-conductivity, 2006, 16(2): 945-948.[2]DENISOV E, DAMOC E, LANGE O, MAKAROV A.Orbitrap mass spectrometry with resolving powers above 1, 000, 000[J]. International Journal of Mass Spectrome-try, 2012(325/326/327): 80-85.[3]NIKOLAEV E N, GORSHKOV M V, MORDEHAI AV, TALROSE V L. Ion cyclotron resonance signal-detec-tion at multiples of the cyclotron frequency[J]. Rapid Communications in Mass Spectrometry, 1990, 4(5): 144-146.[4]GROSSHANS P B, MARSHALL A G. Can Fouriertransform mass spectral resolution be improved by detec-tion at harmonic multiples of the fundamental ion cyclotron orbital frequency?[J]. International Journal of Mass Spectrometry and Ion Processes, 1991, 107(1): 49-81.[5]NAGORNOV K O, GORSHKOV M V, KOZHINOV AN, TSYBIN Y O. High-resolution Fourier transform ion cyclotron resonance mass spectrometry with increased throughput for biomolecular analysis[J]. Analytical Chemistry, 2014, 86(18): 9 020-9 028.[6]ROSE T, APPLEBY R B, NIXON P, RICHARDSON K,GREEN M. Segmented electrostatic trap with inductive,frequency based, mass-to-charge ion determination[J].International Journal of Mass Spectrometry, 2020, 450:116 304.[7]MAKAROV A A. Multi-electrode ion trap: US7767960[P]. 2010-08-03.[8]ZAJFMAN D, RUDICH Y, SAGI I, STRASSER D,SAVIN D W, GOLDBERG S, RAPPAPORT M,HEBER O. High resolution mass spectrometry using a linear electrostatic ion beam trap[J]. International Jour-nal of Mass Spectrometry, 2003, 229(1/2): 55-60.[9]DZIEKONSKI E T, JOHNSON J T, McLUCKEY S A.Utility of higher harmonics in electrospray ionization[10]Fourier transform electrostatic linear ion trap mass spec-trometry[J]. Analytical Chemistry, 2017, 89(8): 4 392-4 397.DING L, BADHEKA R, DING Z, NAKANISHI H. Asimulation study of the planar electrostatic ion trap mass analyzer[J]. Journal of the American Society for Mass Spectrometry, 2013, 24(3): 356-364.[11]DING L, RUSINOV A. High-capacity electrostatic iontrap with mass resolving power boosted by high-order harmonics[J]. Analytical Chemistry, 2019, 91(12): 7 595-7 602.[12]WANG W, XU F, WU F, WU H, DING C F, DING L.Genetic algorithm parallel optimization of a new high mass resolution planar electrostatic ion trap mass ana-lyzer[J]. The Analyst, 2022, 147(24): 5 764-5 774.[13]GREENWOOD J B, KELLY O, CALVERT C R,DUFFY M J, KING R B, BELSHAW L, GRAHAM L,ALEXANDER J D, WILLIAMS I D, BRYAN W A,TURCU I C E, CACHO C M, SPRINGATE E. A comb-sampling method for enhanced mass analysis in linear electrostatic ion traps[J]. Review of Scientific Instru-ments, 2011, 82(4): 1-12.[14]DING L, BADHEKA R. Method of processing imagecharge/current signals: US8890060[P]. 2014-11-18.[15]SUN Q, GU C, DING L. Multi-ion quantitative massspectrometry by orthogonal projection method with peri-odic signal of electrostatic ion beam trap[J]. Journal of Mass Spectrometry, 2011, 46(4): 417-424.[16]SUN Q, GU C, DING L. Quantitative mass spectrometryby orthogonal projection method with periodic signal of electrostatic ion beam trap[J]. International Journal of Mass Spectrometry, 2011, 300(1): 59-64.[17]AUSHEV T, KOZHINOV A N, TSYBIN Y O. Least-squares fitting of time-domain signals for Fourier trans-form mass spectrometry[J]. Journal of the American Society for Mass Spectrometry, 2014, 25(7): 1 263-1 273.[18]SMIRNOV S, RUSINOV A, DING L. Deconvolutionmethod for multiple harmonics FTMS spectra[R]. The 64th ASMS conference, San Antonio, TX, United States,2016.[19]GOLUB G H, van LOAN C F. An analysis of the totalleast squares problem[J]. SIAM Journal on Numerical Analysis, 1980, 17(6): 883-893.[20](Received date :2024-03-12;Revised date :2024-04-02)342质 谱 学 报第 45 卷第 45 卷 第 3 期质 谱 学 报Vol. 45 No. 3 2024 年 5 月Journal of Chinese Mass Spectrometry Society May 2024微波等离子体飞行时间质谱仪研制及元素检测应用研究左 凯1,代渐雄2,赵忠俊1,郭 星2,段忆翔1(1. 四川大学机械工程学院,四川 成都 610065;2. 成都艾立本科技有限公司,四川 成都 611930)摘要:微波等离子体炬(microwave plasma torch,MPT)具有功耗低、操作方便、结构简单等优点,与质谱仪联用可快速分析元素。

Mass

Mass

Resolution
Resolution
Exact Masses of isotopes
High resolution
Exact Mass can provide Molecular Formula With sufficient accuracy, unique molecular formula can be determine
Electron Impact (EI)
Ionization
Volatilization of a sample into the gas phase by heating in a vacuum Bombardment of the volatized sample by a stream of electrons
• Sample which is dissolved in a matrix is ionized by a pulsed laser (CO2 or Nd/YAG) • Soft ionization method • Mass range: up to 500kDa • Suffers from the background interference from the matrix material.
The target is bombarded with a fast atom beam (for
example, 6 keV xenon atoms) that desorb molecular-like
ions and fragments from the analyte.
eXe
Xe+
Xe+ Is accelerated to ~6-10 keV, and pass through Xe

Chapter 14 MS

Chapter 14 MS


That means that you would get a set of lines in the m/z = 160 region. The relative heights of the 158, 160 and 162 lines are in the ratio 1:2:1.


Now substituting the percent abundance of each isotope (79Br and 81Br) into the expansion: 2 2 2 Gives (a b) a 2ab b (4.7)
电子
挥发试样;
CH4 CH4+、CH3+;
+
气体分子 CH4
准分子离子
+
CH4
CH5+、C2H5+
试样分子 XH(M)
XH XH2+、XHCH5+ XHC2H5+、X+;
(M+1)+; (M+17)+; (M+29)+;
相对丰度/(%)
100
149
CO 2C8H1 7 CO 2C8H1 7 EI
100.0% 12C 98.9% 14N 99.6% 16O 99.8% 32S 95.0% 35Cl 75.5% 79Br 50.5% 127I 100.0%
1H
0.8%
0.2% 34S 4.2% 37Cl 24.5%
81Br
18O
49.5%
Br2


Br
Br

79Br:
50.50% 81Br: 49.50%

THE MASS SPECTROMETER

THE MASS SPECTROMETER

THE MASS SPECTROMETERHow a mass spectrometer worksThe basic principleIf something is moving and you subject it to a sideways force, instead of moving in a straight line, it will move in a curve - deflected out of its original path by the sideways force.Suppose you had a cannonball travelling past you and you wanted to deflect it as it went by you. All you've got is a jet of water from a hose-pipe that you can squirt at it. Frankly, its not going to make a lot of difference! Because the cannonball is so heavy, it will hardly be deflected at all from its original course.But suppose instead, you tried to deflect a table tennis ball travelling at the same speed as the cannonball using the same jet of water. Because this ball is so light, you will get a huge deflection.The amount of deflection you will get for a given sideways force depends on the mass of the ball. If you knew the speed of the ball and the size of the force, you could calculate the mass of the ball if you knew what sort of curved path it was deflected through. The less the deflection, the heavier the ball.An outline of what happens in a mass spectrometerAtoms can be deflected by magnetic fields - provided the atom is first turned into an ion. Electrically charged particles are affected by a magnetic field although electrically neutral ones aren't.The sequence is :Stage 1: IonisationThe atom is ionised by knocking one or more electrons off to give a positive ion. This is true even for things which you would normally expect to form negative ions (chlorine, for example) or never form ions at all (argon, for example). Mass spectrometers always work with positive ions.Stage 2: AccelerationThe ions are accelerated so that they all have the same kinetic energy.Stage 3: DeflectionThe ions are then deflected by a magnetic field according to their masses. The lighter they are, the more they are deflected.The amount of deflection also depends on the number of positive charges on the ion - in other words, on how many electrons were knocked off in the first stage. The more the ion is charged, the more it gets deflected.Stage 4: DetectionThe beam of ions passing through the machine is detected electrically.A full diagram of a mass spectrometerUnderstanding what's going onThe need for a vacuumIt's important that the ions produced in the ionisation chamber have a free run through the machine without hitting air molecules.IonisationThe vaporised sample passes into the ionisation chamber. The electrically heated metal coil gives off electrons which are attracted to the electron trap which is a positively charged plate.The particles in the sample (atoms or molecules) are therefore bombarded with a stream of electrons, and some of the collisions are energetic enough to knock one or more electrons out of the sample particles to make positive ions.Most of the positive ions formed will carry a charge of +1 because it is much more difficult to remove further electrons from an already positive ion.These positive ions are persuaded out into the rest of the machine by the ion repeller which is another metal plate carrying a slight positive charge.AccelerationThe positive ions are repelled away from the very positive ionisation chamber and pass through three slits, the final one of which is at 0 volts. The middle slit carries some intermediate voltage. All the ions are accelerated into a finely focused beam.DeflectionDifferent ions are deflected by the magnetic field by different amounts. The amount of deflection depends on:∙the mass of the ion. Lighter ions are deflected more than heavier ones.∙the charge on the ion. Ions with 2 (or more) positive charges are deflected more than ones with only 1 positive charge.These two factors are combined into the mass/charge ratio. Mass/charge ratio is given the symbol m/z (or sometimes m/e).For example, if an ion had a mass of 28 and a charge of 1+, its mass/charge ratio would be 28. An ion with a mass of 56 and a charge of 2+ would also have a mass/charge ratio of 28.In the last diagram, ion stream A is most deflected - it will contain ions with the smallest mass/charge ratio. Ion stream C is the least deflected - it contains ions with the greatest mass/charge ratio.It makes it simpler to talk about this if we assume that the charge on all the ions is 1+. Most of the ions passing through the mass spectrometer will have a charge of 1+, so that the mass/charge ratio will be the same as the mass of the ion.Assuming 1+ ions, stream A has the lightest ions, stream B the next lightest and stream C the heaviest. Lighter ions are going to be more deflected than heavy ones.DetectionOnly ion stream B makes it right through the machine to the ion detector. The other ions collide with the walls where they will pick up electrons and be neutralised. Eventually, they get removed from the mass spectrometer by the vacuum pump.When an ion hits the metal box, its charge is neutralised by an electron jumping from the metal on to the ion (right hand diagram). That leaves a space amongst the electrons in the metal, and the electrons in the wire shuffle along to fill it.A flow of electrons in the wire is detected as an electric current which can be amplified and recorded. The more ions arriving, the greater the current.Detecting the other ionsHow might the other ions be detected - those in streams A and C which have been lost in the machine?Remember that stream A was most deflected - it has the smallest value of m/z (the lightest ions if the charge is 1+). To bring them on to the detector, you would need to deflect them less - by using a smaller magnetic field (a smaller sideways force).To bring those with a larger m/z value (the heavier ions if the charge is +1) on to the detector you would have to deflect them more by using a larger magnetic field.If you vary the magnetic field, you can bring each ion stream in turn on to the detector to produce a current which is proportional to the number of ions arriving. The mass of each ion being detected is related to the size of the magnetic field used to bring it on to the detector. The machine can be calibrated to record current (which is a measure of the number of ions) against m/z directly. The mass is measured on the 12C scale.THE MASS SPECTRA OF ELEMENTSThe mass spectrum for boronThe mass spectrum for zirconiumThe number of peaks in the mass spectrum shows the number of the isotopes for an element.The total mass of these 100 typical atoms would be(51.5 x 90) + (11.2 x 91) + (17.1 x 92) + (17.4 x 94) + (2.8 x 96) = 9131.8The average mass of these 100 atoms would be 9131.8 / 100 = 91.3 (to 3 significant figures).91.3 is the relative atomic mass of zirconium.Note: When you calculate the relative atomic mass for element, the total of % of abundance is 100%.。

质谱技术——精选推荐

质谱技术——精选推荐

MALDI
基质辅助激光解吸离子化
基本原理:将分析物分散在基质分子中形成 晶体,当用激光(337nm氮激光)照射晶体 时,基质分子吸收激光能量,样品解吸附, 基质-样品之间发生电荷转移使样品分子电 离。
MALDI
基质辅助激光解吸离子化
(337nm)
基质的主要特征: ¾对激光有较强的吸收 ¾与样品能溶于同一种溶剂 ¾真空稳定性 ¾一定包容性 −对分析物不能有共价修饰
The X axis is the ratio of mass to charge(m/z). For example, if
the mass of a molecule is 2000 and the molecule posses two
proton adducts, its m/z value is equal(2000+2)/2, the m/z
Ethanol CH3CH2OH
MW=46.1
Mass spectrometry: Determine mass of molecule by observing behavior of its ion(or fragments) in magnetic or electronic field.
ESI的主要特点
¾离子化过程温和 ¾对检测大分子很有意义
Typical ESI Spectrum
MALDI AND ESI
MALDI
固相 高能离子轰击 单电荷离子 基质离子 易操作
ESI
液相 强电场 多电荷离子 污染离子 操作相对复杂
How MS Instruments Work
-----Steen H & Mann M,Nat Rev Mol Cell Biol,2004,5:699
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a rXiv:h ep-th/99615v321D ec1999hep-th/9906105KIAS-P99038Mass Spectrum of D =11Supergravity on AdS 2×S 2×T 7Julian Lee and Sangmin Lee 1School of Physics Korea Institute for Advanced Study Seoul,130-012,Korea ABSTRACT We compute the Kaluza-Klein mass spectrum of the D =11supergravity compactified on AdS 2×S 2×T 7and arrange it into representations of the SU (1,1|2)superconformal algebra.This ge-ometry arises in M theory as the near horizon limit of a D =4extremal black-hole constructedby wrapping four groups of M-branes along the T 7.Via AdS/CFT correspondence,our result gives a prediction for the spectrum of the chiral primary operators in the dual conformal quantum mechanics yet to be formulated.1IntroductionAmong all known examples of the AdS/CFT correspondence[1,2,3,4],the least understood is the AdS2/CFT1case.The D=1conformalfield theory(CFT),or conformal quantum mechanics (CQM),has not been formulated and therefore no quantitative comparison between the two sides of the duality has been made.See[5,6]for proposals on the CQM and[7,8,9,10]for progress made in the bulk theory.One of the most elementary check of the correspondence is to compare the spectrum of the two theories.In particular,the Kaluza-Klein(KK)mass spectrum of the supergravity(SUGRA) on AdS is identified with the spectrum of chiral primary operators in the dual CFT.One may hope that the KK spectrum of a SUGRA on AdS2may give a clue to formulate the dual CQM.The goal of this paper is to compute the KK spectrum in the cases where the AdS2is part of a string/M theory vacuum.We specialize in the example of D=11SUGRA compactified on AdS2×S2×T7.1We consider only the zero modes in T7.From the string theory point of view,this theory is a valid approximation when R>>r,˜r,where r,˜r are the radius and the dual radius of T7respectively,and R is the radius of the sphere.In what follows,we will put R to1for simplicity.To obtain this geometry from M theory,one begin with compactifying M theory on T7 with the following brane configuration[11].2Brane012345678910M2x x xM2x x xM5x x x x x xM5x x x x x xWith suitable choice of the orientation of the branes,this configuration breaks N=8super-symmetry(SUSY)of the D=4theory to N=1.When the number of branes in each group is all equal,the background metric describes a direct product of an extremal D=4Reissner-Nordstr¨o m black-hole and a T7.See section3.of[11]for more details.The AdS2×S2spacetime arising as the near horizon geometry of this black-hole is known as the Bertotti-Robinson metric[12].Note that the brane configuration at hand approaches the Bertotti-Robinson metric in the near horizon limit even when the four charges are not equal.The number of SUSY is doubled in the near-horizon limit as usual,so we have D=4,N=2 SUSY.The super-isometry group of the theory is SU(1,1|2).The KK spectrum form representa-tions of the SU(1,1|2)superalgebra.The methods of the computation used in this paper are well known from higher dimensional ex-amples.There are two approaches to the problem;one is direct SUGRA calculation[14]-[18],andthe other uses representation theory of superconformal algebra together with duality symmetry ofSUGRA[19]-[24].We will adopt thefirst approach and explicitly calculate the spectrum,startingfrom the D=11SUGRA lagrangian.Although we will be mainly interested in the modes whichhave bulk degrees of freedom.However,as was noted in ref.[29],we cannot ignore the boundarymodes completely because one of them forms a multiplet with bulk modes.We will make furthercomments on this point later.This paper is organized as follows.In section2,we review the SU(1,1|2)superalgebra andits representation theory following[19,20].In section3,as a warm-up exercise we compute thespectrum of a toy model,namely the minimal D=4,N=2SUGRA.This model illustratesmany important aspects of the compactification on AdS2×S2in a simple setting.In section4,we present a summary of our main result.In section5and6,we sketch the computation of bosonicand fermionic mass spectrum of the“realistic”model obtained from the D=11supergravity.We focus on the reduction from D=11to D=4and how the N=8supermultiplet break intoN=2multiplets.As this work was being completed,we received[29]which has overlap with section3of thispaper.While this paper was being submitted to hep-th e-print archive,we received[30]whichconsidered the same model in a manifestly U-duality covariant way.2Review of the SU(1,1|2)Superconformal AlgebraThe SU(1,1|2)superconformal algebra is defined by the following commutation relations[L m,L n]=(m−n)L m+n, J a,J b =iǫabc J c,[L m,J a]=0,(2.1a)(σa)αβGβ¯αr,(2.1b) [L m,Gα¯αr]=(12{Gα¯αr,Gβ¯βs}=ǫ¯α¯β{ǫαβL r+s−(r−s)(σaǫ)αβJ a}.(2.1c) and the Hermiticity conditionsL†m=L−m,(J a)†=J a,(Gα¯αr)†=ǫαβǫ¯α¯βGβ¯β−r.(2.2) The bosonic generators L+1,0,−1and J0,1,2generate the SL(2,I R)conformal group and the SU(2) R-symmetry group,respectively.We have eight supercharges all together;Gα¯αcarry L0charge±1/2∓12,1j L0Degeneracyn/2n/2n+1G++−1/2|0 ,G+−−1/2|0(n−2)/2(n+2)/2n−1( a1· a†1+ a†2· a2),L+1= a2· a1(2.3a)2J+= ψ†1· ψ†2,J0=1( a†1· a− a†2· a2)−123We thank Jan de Boer for a correspondence on this point.21Figure1:The complete KK spectrum of the toy model.Each circle in thefigure represents a state which has a definite value of h and j.The crossed circles correspond to the boundary states.The degeneracy(2j+1)of each state is included in the circle.The states belonging to the same SU(1,1|2)multiplet is connected by a dotted line.The two KK towers on the top row satisfy h=j and correspond to chiral primary states..3Toy ModelAs a warm-up exercise,we compute the mass spectrum of the minimal D=4,N=2SUGRA. It is the simplest SUGRA that admits the AdS2×S2solution with the SU(1,1|2)superalgebra. The theory contains a single N=2gravity multiplet whose componentfields are a graviton,a massless vector and a complex gravitino.3.1ResultThe computation in the following subsections show that the KK spectrum of the toy model contains the short multiplets in Table1for all even n.We have two copies of each multiplet for n≥4and one copy for n=2.The result is depicted in Figure1.From the point of view of the SUGRA computation,each physical degree of freedom of the fields in D=4give a KK tower.That explains why we have four bosonic and four fermionic series of states in the spectrum.Depending on the spin and the polarization of a givenfield,the low lying modes(j=0,13.2Bosonic mass spectrum3.2.1SetupWe normalize thefields such that the action reads2κ2S= d4x√4F2−¯ψmΓmnp∇nψp−i2F rsΓrsmn)ψn ,(3.1) up to terms quartic in fermions that are irrelevant to our computation.The bosonic equations of motion consist of the Einstein and Maxwell equations in vacuum.G mn F2,∇m F mn=0.(3.2)R mn=18These equations admit dyonic Reissner-Nordstr¨o m black-hole solutions.The near horizon geom-etry of an extremal black-hole gives the AdS2×S2solution.The radius of the S2is equal to the Schwarzchild radius of the black-hole.For simplicity,we consider an extremal electric black-hole with unit radius only.Then the AdS2×S2solution readsRµνλσ=−(gµλgνσ−gµσgνλ),¯Fµν=2ǫµν,Rαβγδ=gαγgβδ−gαδgβγ,¯Fαβ=0.(3.3) where the Greek lettersα,β···andµν···label two dimensional indices for AdS2and S2respec-tively.The fermions are set to zero.We are interested in the mass spectrum of thefluctuations of thefields around this background.We use the following parametrizations of thefluctuations.Gαβ=gαβ+h(αβ)+1h1gµν,Gµα=hµα,(3.4a)2Fαβ=∇αaβ−∇βaα,Fµν=2ǫµν+∇µaν−∇νaµ,(3.4b) where the paranthesis denotes the traceless part of a symmetric tensor.3.2.2Spherical harmonics decomposition and gauge choiceEachfield can be decomposed into spherical harmonics.Unlike higher dimensional spheres,S2 does not have genuine vector or tensor spherical harmonics.Vector and tensorfields are spanned by derivatives of the scalar spherical harmonics.h(αβ)=φI1∇(α∇β)Y I+φI2ǫγ(α∇β)∇γY I(j≥2),h2=h I2Y I,Y I,h1=h I1Y I,h(µν)=h I(µν)(3.5)hµα=w Iµ∇αY I+v Iµǫαβ∇βY I(j≥1),aα=q I∇αY I+b Iǫαβ∇βY I(j≥1),aµ=a IµY I.The composite index I specifies both the total angular momentum j and the J0eigenvalue m.The restrictions on the value of j for somefields are due to the fact that∇αY(j=0)=∇(α∇β)Y(j=1)=ǫγ(α∇β)∇γY(j=1)=0.(3.6) Not all the modes in the above expansion are physical since the(D=4)graviton and gaugefields are subject to the gauge transformations,δh mn=∇mΛn+∇nΛm,(3.7a)δa m=−¯F mnΛn+∇m(Σ+Λn¯A n).(3.7b)The functionsΛm andΣare also expanded in spherical harmonics.We need to make a choice of gauge.First,consider the case j≥2.We can gauge away h(αβ) completely by a suitable choice ofΛα.We then useΛµto eliminate the w Iµstly,we use Σto eliminate the q I terms.With this choice of gauge,we note that∇αhµα=0,∇αaα=0.(3.8) For j=1,h(αβ)modes are absent,soΛαcan be used to reduce other degrees of freedom.Wefind it convenient to parametrizeΛm andΣasΛ(1)µ=(Kµ+∇µX)·Y,(3.9a)Λ(1)α=P·ǫαβ∇βY−X·∇αY,(3.9b)Σ(1)=Q·Y,(3.9c)where the dot product means the sum over the three components of j=1spherical harmonics.We can use X,Kµand Q to gauge away h1,wµand q,respectively.Under the gauge transformation by P,vµis shifted by∇µP.This indicates that vµis a massless gaugefield in AdS2.Indeed,the mass term for vµis absent as we will see below.Being a gaugefield in D=2,vµhas no propagating degree of freedom in the bulk.Also h2can be locally gauged away by residual gauge symmetry.For j=0,h(µν),h1,h2and aµare the only modes that remain.The gauge parameterΛαis absent.We can useΛµto gauge away h(µν).The vector aµbecomes a gaugefield in AdS2withΣbeing the gauge transformation parameter,and again has no bulk degree of freedom.3.2.3Linearizedfield equationsThe linearized Einstein and Maxwell equations readR(1)mn(h)=¯F l n(∇m a l−∇l a m)+¯F l m(∇n a l−∇l a n)−g mn¯F kl∇k a l−¯F mk¯F nl h kl+14h mn¯F2,(3.10)∇m(∇m a n−∇n a m)−1Among the other six equations,(3.13c)and(3.16a)are constraints,and the other four are dynamical equations for each physicalfield.Wefirst use the constraints to set on shell.4vµ=2ǫµν∇νv,aµ=ǫµν∇νa(3.18) To simplify notations,we are suppressing the superscripts I in the equations from here to the end of this subsection.Inserting these in(3.13a)and(3.16b)immediately yields∇2x h2−(j2+j−2)h2−4∇2x a=0,(3.19a)∇2x b−j(j+1)b−4∇2x v=0.(3.19b) After some manipulations,the other two equations(3.15b)and(3.17)give∇2x v−(j2+j−2)v−b=0,(3.20a)∇2x a−j(j+1)a−h2=0.(3.20b) They are diagonalized by the following linear combinations of thefields.s1=b−2(j+2)v,s2=h2−2(j+1)a,(3.21a)t1=b+2(j−1)v,t2=h2+2ja.(3.21b)They satisfy∇2s i−j(j−1)s i=0,(3.22a)∇2t i−(j+1)(j+2)t i=0.(3.22b) In AdS2,the scaling dimension of the operator corresponding to a scalarfield is given by[2,3]h=11+4m2).(3.23)This implies that thefields s1,2have h=j and are chiral primaries,while t1,2have h=j+2.It remains to analyze(3.14b)and(3.15a).Inserting(3.15a)into(3.14b)and using(3.18),we find∇2x h I(µν)−j(j+1)h I(µν)+2h I(µν)=4∇(µ∇ν)a.(3.24) It is also possible to show that in two dimensions,(3.15a)implies(∇2+2)h(µν)=∇(µ∇ν)(h2+4a)(3.25) It can be derived most easily in a light-cone coordinate and a conformal bining these two equations,wefind that h(µν)is algebraically determined by h2and hence has no degree of freedom.This argument is valid for j=1also,but not for j=0.3.2.5j=1The computation for j=1differs from that for j≥2in two ways.First,h1is removed by a gauge choice rather than the constraint(3.13b)which is absent because∇(α∇β)Y(j=1)=0.Second,vµand h2has no bulk degree of freedom and can be eliminated.The equations can be diagonalized as before,and the three eigenstates are identified with the j=1points of the t1,t2and s2series. The absence of the corresponding point on the s1series is a consequence of the fact that vµis a gaugefield.Note also that s2can be gauged away on shell by a residual gauge degree of freedom. By X in(3.9b)with∇2X=0,s2is shifted to s2+X.Therefore it is also a boundary degrees of freedom.3.2.6j=0We have thefield equations for h1,h2and aµ∇2x(h1+h2)=−4ǫµν∇µaν−2h1,(3.26a)∇2x h2=4ǫµν∇µaν−2h2+4h1,(3.26b)∇ν(∇νaµ−∇µaν)=ǫµν∇ν(h2−h1).(3.26c) Recall that we gauged away h(µν).Its equation of motion then gives a“Gauss law”constraint,∇(µ∇ν)h2=0.(3.27) One can easily show that(in light cone coordinate,for example)the only normalizable solution to the constraint is h2=constant.It is consistent to set h2to zero.We can eliminate the gaugefield aµfrom the h1equation andfind that m2=2.This is identified with the j=0point of the t2 series.This completes the derivation of the bosonic spectrum in Figure1.3.3Fermionic mass spectrumThe linearizedfield equation for the fermion readsΓmnp∇nψp=−i2¯F rsΓmnrs ψn.(3.28) The linearized SUSY transformation law plays the role of a gauge symmetry,that is,the following variation leaves thefield equation invariant:δψm=∇mǫ−i¯F nl 18Γm nl ǫ.(3.29) It is convenient to separate the“trace”and the“traceless”part ofψµandψα.ψµ=ψ(µ)+1Γαη(Γµψ(µ)=Γαψ(α)=0).(3.30)2We decompose the D=4gamma matrices in terms of the D=2gamma matrices as follows:Γµ=γµ⊗1,Γα=¯γ⊗τα(¯γ=γ0γ1).(3.31) Now we can split(3.28)into four components(∇/x+¯γ∇/y)η+¯γ∇/yλ−2∇αψ(α)=−i¯γλ,(3.32a)(∇/x+¯γ∇/y)λ+∇/xη−2∇µψ(µ)=−i¯γη,(3.32b)∇(µ)η+¯γ∇/yψ(µ)=−i¯γψ(µ),(3.32c)∇(α)λ+∇/xψ(α)=+i¯γψ(α),(3.32d) where thefirst two equations are the traceless parts of theµandαcomponents of(3.28),respec-tively.The other two are the trace parts.Here,∇/x,∇/y are the two dimensional dirac operators.The gauge transformation law also divides into four pieces.δψ(µ)=∇(µ)ǫ,δλ=∇/xǫ−i¯γǫ,(3.33a)δψ(α)=∇(α)ǫ,δη=¯γ(∇/yǫ+iǫ).(3.33b)Consider the spherical harmonics decomposition.λ=λI+ΣI++λI−ΣI−,ψ(µ)=ψI(µ)+ΣI++ψI(µ)−ΣI−,η=ηI+ΣI++ηI−ΣI−,ψ(α)=ψI+∇(α)ΣI++ψI−∇(α)ΣI−,ǫ=ǫI+ΣI++ǫI−ΣI−.(3.34)See Appendix B for the definition and properties of spinor spherical harmonics.For j≥3/2,it is clear that one can gauge awayηcompletely.Then(3.32c)setsψI(µ)=0.In turn,wefind in (3.32b)thatλsatisfies the eom for a free massless spinor in d=4.Finally,(3.32a)determinesψ(α) algebraically in terms ofλ.As a consistency check,we substitute it into(3.32d)andfind the same eom forλ.Thus all that remains is tofind the mass spectrum ofλ.After the spherical harmonics decomposition,the equation reduces to∇/λ++i(j+12)¯γλ−=0.(3.35) The mass eigenstates areξ1=(1+i¯γ)E andξ2=(1−i¯γ)F both of which have m=j+12ταΣ±=⇒∇/yΣ±=±iΣ±.(3.36)It has three consequences.First,modes forψ(α)are absent.Second,(3.32d)is trivially satisfied. Finally,the gauge variation ofη−vanishes for arbitraryǫ−.We choose to gauge awayη+andψ(µ)−usingǫ+andǫ−,respectively.With these in mind,we analyze the threefield equations.From the coefficients ofΣ+in(3.32a)and(3.32c),wefind thatλ+=0,ψ(µ)+=0.(3.37)The coefficients ofΣ−of the same equations yield(∇/x−i¯γ)η−=0,∇(µ)η−=0.(3.38) These two equations together imply thatη−has no propagating degree of freedom and can be set to zero consistently.Finally(3.32b)gives(∇/x−i¯γ)λ−=0,(3.39) which we recognize as the j=1/2point of theξ2series.The scaling dimension of the operator corresponding to a spinorfield in AdS2is given byh=|m|+1210Hyper multiplet210Vector multiplet21Gravitino multipletGravity multiplet210Figure 2:The KK spectrum of the D =11SUGRA on AdS 2×S 2×T 7.12Boundary degrees of freedom can arise in the gravitino multiplet as well,but are not determined by the computation here.In the following two sections,we explain the dimensional reduction of the field equations from D =11to D =4,how different fields fall into N =2multiplets and how each multiplet produces the KK spectrum given in Figure 2.5Bosonic Mass Spectrum5.1SetupWe normalize the fields such that the action reads2κ2S = d 11x √2·4!F 2−¯ΨI ΓIJK ∇J ΨK +1−G12·3!F MIJK F N IJK −12·4!·4!ǫIJKL 1L 2L 3L 4M 1M 2M 3M 4F L 1L 2L 3L 4F M 1M 2M 3M 4.(5.2b)The AdS 2×S 2×T 7solution is given byds 211=g µνdx µdx ν+g αβdx αdx β+δab dz a dz b +δst dw s dw t,R µνλσ=−(g µλg νσ−g µσg νλ),R αβγδ=g αγg βδ−g αδg βγ,¯Fµν45=¯F µν67=ǫµν,¯F αβ46=¯F αβ75=ǫαβ.(5.3)All other fields are set to zero.This is the near horizon geometry of the brane configuration shownin the introduction.The notational conventions for the indices are summarized in Appendix A.Note that the background fields are self-dual in the SO (4)for the four coordinates along which the branes lie.Equivalently,it transforms in the (0,1)representation of SO (4)≃SU (2)+×SU (2)−.This follows from the requirement of partially unbroken supersymmetry.If any one of the relative sign for the gauge field is flipped,the supersymmetry is completely broken,even though it is still a solution to the equations of motion.6This background breaks the SO (7)isometry of the internal T 7down to SU (2)+×SU (2)3,where SU (2)3is the rotation of w 8,9,10.These internal symmetries will play a crucial role in grouping the fields,as will be shown in the next section.5.2Linearizedfield equations and reduction to D=4We linearize the equations in D=11influctuations around the background,G MN=g MN+h MN,F IJKL=¯F IJKL+4∇[I a JKL],(5.4)and then dimensionally reduce it to D=4by keeping only the zero modes of thefluctuations in internal T7=T4×T3.We then redefine some of thefluctuationfields,=h(4)mn−1h(11)mnǫklmn¯F ab kl W b mn,(5.8)4where W a mn is thefield strength of V a mn.The equation remains valid when a is replaced by s,except that in this case the right-hand side vanishes.The quantum numbers of the variousfluctuationfields with respect to the internal symmetries are summarized below,along with that of the background gaugefield¯F ab ing this table,one can divide thefields into small groups,where thefields belonging to the same group can couple to each other.Thefields within a group must have the same quantum numbers except the broken SU(2)−charge,which can be shifted by1by the backgroundfield.We label these groups by capital roman letters.Note that we separated the self-dual and the anti-self-dual parts of thefields which are rank two tensors in SO(4)byA ab±≡1SU(2)+SU(2)−Grouph mn0V a m000B11E 3B a a+2B s s01/21/2C B(st)200FA ab+m10EA as m100B1/21/2D C sab+110AC ast100F1/21/2DD s101The linearized equations of motion in D=4are given byGroup A∇2C sab+=14ǫklmn¯F ab kl F s mn,(5.11a)∇n F s nm=−12ǫstu F tu mn),(5.11b)∇n W s nm=1∇2C as=12ǫstu C atu),(5.12a)∇2B as=12ǫm nkl¯F ab nk∇l C bs.(5.12c) Group D2W[a mn¯F bc]mn,(5.13a)∇2D a=12ǫm nkl¯F ab nk∇l D b+1∇2B(ab)=12F bc−mn¯F ca mn+1∇2C=12¯F abmnF ab+mn−12¯F abmn(2∇k h kn−∇n h k k−∇n B s s)+12¯F abmkF ab+nk+16g mn¯F ab kl F ab+kl−16g mn¯F ab kj¯F ab kl h jl+16∇2B s s.(5.15d)165.3Computation of mass spectrum in each multipletWe have separatedfields which decouple from one another using their internal quantum numbers. We should now disentangle thefield equations further andfind out whichfield belong to which N=2multiplet.Obviously,the bosonicfields in the same multiplet satisfy the samefield equa-tions,and the same for the fermions.In this section,we jump to solve the equations of motion offields in each multiplet,except for the gravity multiplet which has been analyzed in detail in section3.The reduction of the equations obtained in the previous subsection to thefinal form require somewhat lengthy algebra, and we put it off until the next subsection.The complication partly arises from the fact that we chose a specific D=11configuration from the beginning.Although the M theoretic origin of the geometry is manifest in this framework,the U-duality invariance of the D=4theory and its symmetry breaking pattern is obscured.A manifestly duality invariant approach sketched in[21] could simplify the process to a large extent.5.3.1Hyper multipletMinimally coupled scalars in D=4belong to this multiplet.Clearly,the KK modes have m2= j(j+1).It follows that h=j+1.There is no gauge symmetry associated with the scalars.5.3.2Vector multipletA vector multiplet contains a vector A m and two real scalarsφ1,φ2.In the simplest case,φ1couples to Aαonly andφ2to Aµ.Thefield equations for thefirst group are(∇2x+∇2y−2)φ1=1For j=0,b is absent andφ1has m2=2,h=1.Thefield equations forφ2and Aµare(∇2x+∇2y+2)φ2=1All thefields in this group are minimally coupled scalars in D=4and belong to the hyper-multiplet.Group Bǫmn kl F s kl−¯F ab mn C sab+.(5.23)2Then the equation of motion of F s becomes the Bianchi identity for˜F s,and the Bianchi identity for F s become∇n˜F s nm=¯F ab mn∇n C sab+.(5.24)18Note that the right-hand side is the same as that of(5.11c).In terms of˜F s,thefield equation for C becomes∇2C sab+=1Writing down all the components of thefield equations and collecting those which couple to one another,onefinds twelve identical copies of the following set of coupled equations:∇2B=−∇2C=1If we defineC a=1First,B45+B67,B46−B75and B44−B55−B66+B77decouple and contribute to the hyper multiplet.The other equations fall into six groups each of which contains one scalar and one vector. Each group gives the spectrum for half a vector multiplet.Explicitly,the six groups are(B44+B55−B66−B77,A45−µ),(B44−B55+B66−B77,A46−α),(5.28)),(B45−B67,A47−α),(B46+B75,A47−µ(B47−B56,A46−µ),(B47+B56,A45−α).Group Fgrav vec Total 0018B442448D6301215F 20Sum2440Table 3:This table summarizes the number of degrees of freedom a group of bosonic equationscontribute to each of the four multiplets..First,h 2≡h αα,B ss ,A 45+µand A 46+αbelong to the gravity multiplet.Second,h µα,A 46+µand A 45+α,C belong to the vector multiplet.Finally,A 47+µand A 47+αdecouple and contribute to the gravitino multiplet.6Fermionic mass spectrum6.1Linearized field equations and reduction to D =4The linearized field equation for the gravitino in D =11readsΓIJK ∇J ΨK =18ΓJK ΨL F I JKL .(6.1)Throughout this section we suppress the bar on the background field strength.The linearized local SUSY transformation law plays the role of gauge symmetry for Fermions:δΨM =∇M ǫ+14Γa λ,χ=Γs Ψs ,Ψ(s )=Ψs −12Γm (λ+χ).(6.4)We then decompose the fermion into chiral and anti-chiral components with respect to SO (4)of T 4,Ψ±≡1SU (2)+SU (2)−Group 1/2IΨ−m Ψ+(a )1/21/21I 1/2G(3λ+2χ)−Ψ+(s )3/201/2H 1/2Iχ−Table 4:Internal quantum numbers of the fermionic fields..where ¯Γ≡1Γn ∇n Ψ+(s )=Γn ∇n (3λ+2χ)+=0,(6.6a)δΨ+(s )=δ(3λ+2χ)+=0.(6.6b)Group H4F ad ij Γij Ψ+(d ),(6.7a)Γn ∇n (3λ+2χ)−=116F cd ij Γij Γcd Ψ−(s ),(6.7c)δΨ+(a )=δ(3λ+2χ)−=δΨ−(s )=0.(6.7d)Group I8F ab ij Γb {Γij χ++(Γijk −2Γi δjk)Ψ+k },(6.8a)Γmnk ∇n Ψ+k=−14F ab ij Γij Γa Ψ−(b ),(6.8c)δΨ−(a )=1Group JF cd ijΓcd(Γijk−2Γiδjk)Ψ−k,(6.9a)16Γmnk∇nΨ−k=132F ab ij(Γmij−2δmiΓj)Γabχ−,(6.9b)δΨ−m=∇mǫ−−1F ab ijΓabΓijǫ−.(6.9d)166.2Computation of the mass spectrum in each multiplet6.2.1Hyper multipletSpinors with nonzero mass generated by the background gaugefield belong to this multiplet.After diagonalizing the mass matrix,they satisfy the equation of motion of the formΓm∇mψ+iΓ01ψ=0.(6.10) Onefinds that|m|=j+1=j+1for all j≥12transformation laws are given byδψ(µ)=∇(µ)ǫ,δλ=∇/xǫ,(6.12)δψ(α)=∇(α)ǫ,δη=¯γ∇/yǫ,δχ=−i¯γǫ.One can always gauge awayη.Then(6.11d)setsψ(µ)to zero.For j≥3/2,(6.11b)determineψ(α)algebraically.The only independent equations that remain are(6.11a)and(6.11c)withηandψ(µ)removed.The mass eigenvalues are the same as those of hyper multiplet:|m|=j+1All the spinors in this group are massless and minimally coupled in D=4and belong to the vector multiplet.Group H(σ1⊗Γ01+σ2⊗Γ23)Ψ.(6.15)2We can further decompose the equation by settingΨ= Ψ1Ψ2 .(6.16) After splitting each ofΨ1,2into two pieces according to their chirality in the non-compact D=4 spacetime,and recombining those pieces which couple to each other,onefinds that one linear combination belongs to the vector multiplet and the other one to the hyper multiplet.except that it has twice as many degrees of freedom The spectrum is exactly the same forΨ+(s)as3λ+2χ.Wefind the same result even forΨ+again except for the degeneracy.In counting(a)the degeneracy,one should remember the constraintΓaΨ(a)=0.In the basis we chose above,it reduces toΨ(4)−iσ1Ψ(5)−iσ2Ψ(6)−iσ3Ψ(7)=0.(6.17) Group I1.A half ofχ−decouple and belong to the vector multiplet.2.A half ofΨ−m decouple and satisfy the same equation as the gravitino in the toy model.Therefore they belong to the gravity multiplet.3.The other components ofχ−andΨ−m couple to each other.They contribute to the spin3/2multiplet.The following table summarizes the result of this section.ACKNOWLEDGEMENTWe are grateful to Seungjoon Hyun for many helpful discussions,Youngjai Kiem for carefully reading the manuscript and making useful comments,and Jan de Boer for a correspondence.SL would like to thank Jeremy Michelson for discussions at Carg`e se’99ASI.grav vec Total02424H0240840J80Sum2440Table5:Summary of the fermionic spectrum.A Notations and ConventionsWe consider D=11SUGRA on AdS2×S2×T4×T3.Each manifold in the product is parametrized by xµ(µ=0,1),yα(α=2,3),z a(a=4,5,6,7)and w s(s=8,9,10),re-spectively.We use the indices(M,N,···)to label all eleven coordinates together and(m,n,···) to label the coordinates of AdS2×S2.The signature of the metric is(−+···+).Thefield strength of a p-form potential in any dimension is defined byF M0···M p =p∇[MA M1···M p].(A.1)B Spherical HarmonicsThe spherical harmonics form a basis for thefields living on a sphere.In this appendix we consideronly the case of S2.We can construct them by considering the eigenstates of maximal commutingsubalgebra of SU(2)group,which are the total angular momentum J2=j(j+1),its z componentJ z=m,the orbital angular momentum L2=l(l+1),and the spin S2=s(s+1).The case forthe scalar is easiest since s=0and J2= L2,which we identify with the Laplacian on the sphere,∇2y,where y indicates two dimensional coordinates parametrizing the two-sphere.This expression for L2can be obtained by embedding S2into three dimensional space,writing down L2in termsof the Cartesian coordinates,which is quite well known,and reexpressing these in terms of polarcoordinates.Therefore,by construction,we have∇2y Y(j,m)(y)=−j(j+1)Y(j,m)(y),(B.1) where Y(j,m)(y)denotes the eigenstates with eigenvalues(j,m),which were defined above.Next consider the spinor spherical harmonics where s=1/2.The easiest way to consider itis to embed the sphere in the three dimensional space and use cartesian coordinates.We constructthem by taking the tensor product of scalar spherical harmonics with2-component spinor,and。

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