The fragmentation pattern contains clusters of peaks 14 mass units apart which represent loss of ch2nch3. Mass spectral interpretation is the method employed to identify the chemical formula, characteristic fragment patterns and possible fragment ions from the mass spectra. A split producing a tertiary carbocation will be more successful still. The ir spectrum of x shows peaks at 3300 cm 1, 30002850 cm 1, and 2250, cm 1. Mass spectrometry introduction a mass spectrum can be thought of as being the record of the damage done to a molecule when it is bombarded in the gas phase by a beam of electrons. The integral molecular weight is the sum of the light isotopes of the atoms that make up the molecule. Predicting molecular formulas of fragment ions with isotope patterns in tandem mass spectra. At the moment i am looking at a mass spectrum for paracetemol 4hydroxynethanoylaminobenzene which has four main mz peaks at around 43, 80, 110 and 151. This pattern results in the familiar grouping of fragments spaced 14 units apart with the largest fragment in the cluster resulting from the cnh 2n1 o 2 ion figure 6.
In mass spectrometry, one generates ions from a sample to be analyzed. Mass spectral interpretation is the method employed to identify the chemical formula, characteristic fragment patterns and possible fragment ions from the mass. Instruments can have a range of sensitivities resolving power. I am used to reading mass spectrums of elements with giant atomic stuctures e. The fragment types listed above are the most common fragments observed with ion trap, triple quadrupole, and qtof mass spectrometers. The techniques included their synthesis procedures, fastatom bombardment fab, and lcmsms mass. A tentative identification of components in the essential oil of cannabis sativa l. The heaviest peak with a reasonable abundance is usually the molecular ion.
How to draw molecular fragments based on mass spectrum. Give one fragment in the mass spectrum and one peak in the ir spectrum that could be used to distinguish between these two isomers. Its kind of an odd structure, but actually fairly common. How many molecular ion peaks parent ion peaks occur in the mass spectrum of 1,2dibromoethane, ch2brch2br. Early works on the mass spectrum fragmentation pattern of pyrazoles date from the early 1970s. The mz value of the molecular ion is the same as the molar mass of the sample compound.
Applying the logic of this to fragmentation patterns, it means that a split which produces a secondary carbocation is going to be more successful than one producing a primary one. At the moment i am looking at a mass spectrum for paracetemol 4hydroxy n ethanoylaminobenzene which has four main mz peaks at around 43, 80, 110 and 151. Primary amides show a base peak due to the mclafferty rearrangement. How to determine fragment of compounds in mass spectro. Mass spectra of cyclic ethers formed in the lowtemperature. In the second part of the chapter, the molecular fragmentation for. There would be a major peak in the mass spectrum for butan1ol, ch3ch2ch2ch2oh, but not for butan2ol, ch3ch2chohch3, at me value a 15 b 17 c 29 d 43 so, to begin with, how are we supposed to know how these break apart. The key is to remember a few diagnostic fragment ions e. The peaks due to heavy fragments in the mass spectrum of mo2o2cch34 show that this compound is a dimer. Use the back arrow to return to a spectroscopy problem return to mass spectrum home page. If two peaks differ by 15 units, this is often an indication that the fragments only differ by a.
Top, mass spectrum electron ionization, references data from nist standard reference database 69. The most common peptide fragments observed in low energy collisions are a, b and y ions, as described in the figure above. Follow the link to see the fully annotated fragmentation nomenclature as proposed by biemann. Mass spectrometry fragmentation patterns chemistry. Fragmentation of carboxylic acids in eims molecular ions are of moderate abundance and the most typical fragmentation pathways are the mclafferty rearrangement as well as ccbond cleavage some distance from the functional group. Assume that all the compounds contain c and h and that o may or may not be present. This carbocation can then undergo stepwise cleavage down the alkyl chain, expelling neutral twocarbon units ethene.
The ratio found in the peak pattern is the result of natural isotope abundance of the atoms in the molecule. Mclafferty, interpretation of mass spectra, university science books, mill. Fragmentation of protonated amides through intermediate. Read 11 answers by scientists with 3 recommendations from their colleagues to the question asked by nagham mahmood aljamali on apr 11, 2016.
It is not possible to identify every peak in a mass spectrum. The main piece of information to remember in answering these types of questions is that each of the structures you draw must be positively charged. In 2,2dimethylpentane, the base peak will be at mz 59 in 2methylbutane, both peaks will have comparable intensity in pentane, the base peak will be at mz 43 the structures of the three pentane isomers are mass spectroscopic fragmentation tends to occur at a branch. H3c ch ch 2methylpentan3one 3methylpentanal diagnostic fragment or peak by preceding the value with the letter of the compound, i. The fragmentation of the aromatic nucleus is somewhat complex, generating a series of peaks having me 77, 65, 63, etc. How to determine fragment of compounds in mass spectro i. Fragmentation of organic ions and interpretation of ei mass. Solved predict the masses and the structures of the. Lecture notes in eimass spectrometry by torben lund. The radical cation that is produced when an electron is knocked out of a neutral closedshell molecule in eims initially possesses a lot of energy. Mass spectra and ir mass spectrometry measuring the m r of an organic molecule if a molecule is put through a mass spectrometer it will often break up and give a series of peaks caused by the fragments.
Convert neutral atoms or molecules into a beam of positive or negative ions 2. Fragmentation of nheptane ions by photodissociation. Branched hydrocarbons form more stable secondary and tertiary carbocations, and these peaks will tend to dominate the mass spectrum. Fragmentation of protonated amides through intermediate ion. Chemistry analytical chemistry mass spectrometry, book edited by. The base peak is the peak caused by the most stable or kinetically accessible cation in the ion stream. Analysis of such fragments provides information on the structure of molecules. Purchase interpretation of mass spectra of organic compounds 1st edition. The neutral fragments, being uncharged, are not detected in the mass spectrometer, but the smaller positive ions are. Hrms shows that ion at mz 161 base ion corresponds to formula c 8 h 5 n 2 o 2, so stabilized iminium ion a structure is assigned. Every sample has its own characteristic mass spectrum. Mass spectra analyses of amides and amide dimers of steviol. Simple alkanes tend to undergo fragmentation by the initial loss of a methyl group to form a m15 species.
The following chapter introduces one of the key disciplines of organic mass spectrometry. The field desorption mass spectrum of the mass2000 polypropylene glycol. The other peaks in the spectrum are caused by the fragmentation of molecular ions. Table of common fragment ions wake forest university. Peptide modeling for identification depends strongly on counting the number of predicted fragments that are found in a spectrum, so setting this value correctly will determine the success or failure of an identficiation. A mass spectrometer a mass spectrometer is designed to do three things 1. If the trial formula is c c h h o o n n then the number of double bonds and rings is. A mechanism is proposed for the loss of alkyl radicals where the cleavage of a c c bond is coupled with the rearrangement of a hydrogen atom, thus yielding a secondary alkyl ion that eventually fragments further by a subsequent loss of olefin.
Tandem mass spectra were acquired at a setting of 30% normalized collision energy of the precursor ions at mz 324. The most important information obtainable from a mass spectrum is the integral molecular weight of the compound. The ab pairs are separated by 28u, the mass for the carbonyl, co. The field desorption mass spectra of the mass3000 and. Mass spectrometry and interpreting mass spectra compound. To construct the spectral library, the known endogenous human metabolites in the human metabolome database hmdb 8,021 metabolites and their predicted metabolic products via one metabolic reaction in the. Molecular ion peaks are present, possibly with low intensity. Electron ionization and fragmentation of organic ions and interpretation of ei. Give one fragment in the mass spectrum and one peak in the ir spectrum that could be used to distinguish between these two i h2c ch a.
When students ask what books to read on mass spectrometry, there are various excellent monographs. The lists given above are by no means exhaustive and represents only the simplest and most common fragments seen in the mass spectrum. Each fragment is characterised by the masstocharge ratio, mz. Usually, theyre the result of a single bond in the molecular ion breaking, forming smaller positive ions and neutral fragments. Please see the following for information about the library and its accompanying search program. International journal of mass spectrometry and ion processes volume 72, issues. We report an analytical tool to facilitate metabolite identification based on an msms spectral match of an unknown to a library of predicted msms spectra of possible human metabolites. Mass spectrum of paracetemol organic chemistry science forums. In this case, the fragment at mz 43 is the most abundant ion, and that peak is therefore called the base peak and assigned a value of 100%. As a result, chemical ionization would need to be utilized to determine the molecular mass is 74. The appearance of this type of peak arrangement at the high end of the mz scale on the mass spectrum is characteristic of the molecular ion. All mass spectra in this site plus many more are available from the nistepanih mass spectral library. The ir spectrum of x shows peaks at 3300 cm1, 30002850 cm1, and 2250, cm1. Nist chemistry webbook the national institute of standards and technology nist uses its best efforts to deliver a high quality copy of the database and to verify that the data contained therein have been selected on the basis of sound.
First, the fundamental notions of mass spectrometry are explained, so that the reader can easily cover this chapter graphs, main pick, molecular ion, illogical pick, nitrogen rule, etc. However, there is not a single peak corresponding to the molar mass of mo2o2cch34, instead there is a family peaks. Fragment identificator fid is an windows application for identification of molecular fragments from tandem mass spectrometry data when molecule and spectrum are given. Mass spectrometry liskeard school and community college. May 07, 2015 the other peaks in the spectrum are caused by the fragmentation of molecular ions. The chapter includes an introduction to the main ionisation techniques in mass spectrometry and the way the resulting fragments can be analysed. The detector records the mass spectrum which is a measure of the number of ions of a particular mass. Draw the fragments responsible for the peaks in the mass spectrum at mz 71, 58, and 43. In order to calculate yields, you work out the number of moles of your product by dividing the mass you obtain by the molar mass. Common fragmentation processes for organic molecules are the mclafferty rearrangement and alpha cleavage. Electron impact mass spectra are available for very few of them, making their detection.
A mass spectrum records the masscharge mz values and the relative abundance for all fragments present. In the past 30 years, mass spectrometry ms has undergone a spectacular devel. The most common fragments for alcohols are often associated with. Mass spectrometry of aromatic cyclic imides and amides. This is caused by a different ion than the corresponding peak in the pentane mass spectrum. Separate the ions on the basis of their masstocharge ratio mz 3.
The greater the sensitivity, the finer the difference in masscharge they can resolve. The greater the sensitivity, the finer the difference in mass charge they can resolve. Nov 03, 2005 i am used to reading mass spectrums of elements with giant atomic stuctures e. The leading scientist in this field was fred mclafferty who together with frantisek turecek has written a very famous text book. Fragmentation of nheptane ions by photodissociation sciencedirect. Tandem mass spectrometry 1, 2has assumed increasing importance in recent years as a practical means for the structural elucidation of peptides 3, 4, 5.
Otherwise, the fragment is ignored, without penalty. Mass spectra is a plot of relative abundance against masstocharge ratio. Collisions also affect the interpretative value of the mass spectrum preventing identification. Ions with a smaller mz ie lighter ions are deflected more than those with a larger mz ie heavier ions. You then need to work out the number of moles of complex you started with.
Predicting molecular formulas of fragment ions with. Mass spectrometry and determining organic structures. Mass spectral fragments of common hydrocarbons mass spectral peaks can be identified to have originated from the fragmentation of specific hydrocarbon sources including. Isotopic percentage and nominal mass calculation are also. Mass spec fragmentation an extremely useful result of ei ionization in particular is a phenomenon known as fragmentation. The b ions appear to extend from the amino terminus, sometimes. Mass spectrum of paracetemol organic chemistry science. The spectrum recognized as an alcohol by the m oh peak and is easily discernable by the single prevalent peak at m ch 3. Interpretation of mass spectra of organic compounds 1st. The process is carried out in an instrument known as a mass spectrometer. The peak with the largest mz, however, will be due to the complete molecule and will be equal to the m r of the molecule. Aromatic acids, in contrast, yield benzoyl ions by ho. Mass spectra analyses of amides and amide dimers of.
The peaks due to heavy fragments in the mass spectrum of mo2o2cch3. On a high resolution machine, the compounds c3h6o2 and c4h10o which have relative. The mass spectra of a series of stevioside analogues including the amide and dimer compounds of steviol, isosteviol, and steviolbioside were examined. To evaluate a metabolite spectrum match msm, midas first enumerates possible fragments from a metabolite by systematic bond dissocn. The mixture of intact molecular ions and fragment ions is subsequently massanalyzed. It is commonly used for the identification of organic compounds from electron ionization mass spectrometry. Even when compounds only contain elements with less intense isotope peaks carbon or oxygen, the distribution of these peaks can be used to assign the spectrum to the. Each ms and ms n spectrum was acquired and averaged within 1 min. Trends for pyrazole fragmentation determined by gas.
A label more consistent with the iupac green book and iso 31 conventions is mq or mq where m is the symbol for. Fragmentation of organic ions and interpretation of ei. The two higher mass peaks are due to the presence of isotopes of the compounds atoms. Positive ion mass spectral fragmentation of new steviol, isosteviol, and steviolbioside amides and the amide dimers are reported and discussed. Ch o ch o h3c h3c h3c ch 3,3dimethylbutanal 4methylpentan2one designate which compound will show that diagnostic fragment or peak by preceding the value with the letter of the compound, i.
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