Chemical derivatization processes applied to amine d

81 Pages·2015·1.3 MB·English

Płotka-Wasylka, J. M., Morrison, C., Biziuk, M., and Namieśnik, J. (2015)
Chemical derivatization processes applied to amine determination in
samples of different matrix composition. Chemical Reviews, 115(11), pp.
4693-4718.

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Chemical derivatization processes applied to amine
determination in samples of different matrix composition

Journal: Chemical Reviews
Manuscript ID: cr-2013-006999.R5
Manuscript Type: Review
Date Submitted by the Author: 21-Mar-2015
Complete List of Authors: Płotka-Wasylka, Justyna; Gdańsk University of Technology, Chemical
Faculty, Department of Analitycal Chemistry
Morrison, Calum; University of Glasgow,
Biziuk, Marek; Gdansk Uviversity of Technology,
Namiesnik, Jacek; Gdansk University of Technology, Department of
Analytical Chemistry

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Chemical derivatization processes applied to
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amine determination in samples of different
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matrix composition
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20 Justyna M. Płotka-Wasylka a,*, Calum Morrison b, Marek Biziuk a, Jacek Namieśnik a
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23 aDepartment of Analytical Chemistry, Faculty of Chemistry, Gdansk University of Technology,
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11/12 Narutowicza Street, 80-233 Gdansk, Poland
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bForensic Medicine and Science, School of Medicine, College of Medical, Veterinary and Life
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31 Sciences, University of Glasgow, Glasgow G12 8QQ, UK
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*Corresponding author: Tel.: [phone]; Fax: [phone]; E-mail:
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40 [email protected]
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6 Table of Contents
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1. Introduction
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11 2. Improvement of chromatographic properties by analyte structure change
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13 3. Modes of derivatization of amine compounds in chromatography
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3.1.In situ derivatization
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3.2.Pre-column derivatization
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20 3.3.On-column derivatization
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22 3.4. Post-column derivatization
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4. Derivatization coupled with microextraction techniques
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27 4.1. Solid phase microextraction
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29 4.2. Stir bar sorptive extraction
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4.3. Single drop microextraction
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34 4.4. Hollow-fiber liquid phase microextraction
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36 5. Derivatization reagents for the determination of amines by gas chromatography
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6. Derivatization reagents for the determination of amines by liquid chromatography
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7. Literature data on the procedures of amine compound determination in samples of different
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43 origin and characterized by a diverse matrix composition
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45 8. Conclusions
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Author Information
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50 Corresponding author
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52 Notes
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Biography
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57 Acknowledgements
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59 References
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6 1. INTRODUCTION
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Compounds containing an amino group are widely found in nature1,2 and may be formed
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11 from industrial processes, with important examples being amino acids, triethylamines, anilines
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13 and biogenic amines. Biogenic amines are formed as a result of neutral and basic amino acid
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decarboxylation or by amination of aldehydes and ketones and include catecholamines
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(dopamine, norepinephrine and epinephrine), imidazoleamines (histamine), indoleamines
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20 (serotonin and melatonin) and polyamines (putrescine, spermidine and spermine)3,4. These
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amines are neurotransmitters, hormones, bio-modulators in the Animalia kingdom. It is known
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that both strong tastes and smells associated with decomposing organisms or with certain plants
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27 and fungi may originate from amines. For example, fungi and flowers release a specific smell
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29 whose role is to attract insects or other species5 and the smell coming from decaying fish is
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associated with trimethylamine due to the breakdown of amino acids in the protein rich tissue5.
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34 Amines are also found in aquatic environment, soil and air where many organisms are capable of
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36 producing and releasing amines. For instance, in the freshwater environment, putrescine and
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phenethylamine can occur in phytoplankton. Many precursors to amines (including amino acids)
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are released by aquatic organisms either while alive, or during decomposition of deceased plants
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43 and animals6. These processes are likely to represent an important in situ source of amines to
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aquatic ecosystems.
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Biogenic amines are found in a broad range of food products; particularly in protein-rich
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50 foods of both animal and plant origin but also in fermented products generally7. For instance, in
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52 wine, biogenic amines arise from two sources: raw materials and fermentation processes with the
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main source being of microbial origin, produced during malolactic fermentation by the
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57 decarboxylation of amino acid precursors7. Although, many biogenic amines including
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59 histamine, putrescine and tyrosine are needed for many essential functions in humans and
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6 animals, consumption of food containing high amounts of these amines can have toxicological
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effects.
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11 Amines are also important components of the plant kingdom and many are relevant to
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13 human health. Nicotine derived from tobacco plants (e.g. Nicotiana tabacum L.,Nicotiana
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sylvestris, Nicotiana rustica L.), is a prime example. It is a nicotinic acetylcholine receptor
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agonist and by a variety of mechanisms nicotine is both addictive and a mild antidepressant.
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20 Cocaine is a serotonin – norepinephrine – dopamine re-uptake inhibitor. Accordingly it is a
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22 powerful stimulant, addictive and the basis of the drug trade. Ephedrine from Ephedra sp and
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Taxus sp is a sympathomimetic stimulant that is found in many over the counter decongestants.
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27 In addition to natural source of amines released into the environment, anthropogenic
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29 source should also be mentioned. While critical to living things, amines are also used and
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31 produced by the chemical industry1,2. For example, they are used as components in personal care
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34 products (e.g. aminomethyl propanol), detergents for laundry and dishwashing, disinfectants and
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36 degreasers (e.g. monoethanolamine)8. Amines are also used in chemical herbicides and pesticides.
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38 For example, monoethanolamine is used as an organic chelating agent used to reduce activity of
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elevated antioxidant enzyme levels in bi-pyridylium resistant plant species biotypes to overcome
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herbicide resistance. Amines including methylamine, ethylamine, n-butylamine are important raw
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45 materials in the production of pigments, medicines, corrosion inhibitors and polymers. The
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47 majority of these compounds are characterized by toxicity and allergenic properties. Moreover,
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they show adverse influence on eye mucus membrane, skin and the respiratory system.
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52 Additionally, amines can react with nitrites to form carcinogenic nitrozo amines1.
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54 The previous discussions show the relevance of amines to the well-being of both animals
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and humans. There is a need for analytical methods that detect these analytes in biological,
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59 environmental, forensic and food samples. High sensitivity and selectivity are a prime
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6 requirements of such methods. These requirements, however, have to be met under the
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constraints of costs and environmental stewardship.
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11 In practice, a variety of analytical methods are used in order to determine amine content
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13 in biological or environmental samples9. Gas and liquid chromatography have been used to a
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15 greater extent than other analytical techniques1. However, as many amines are polar, gas
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chromatography is not suitable for determination for this class of compounds. In addition many
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20 important amines do not possess structural features the enable detection by HPLC with a variety
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22 of detectors such as a ultraviolet absorption, fluorescence, electrochemical reduction/oxidation or
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even mass spectrometry. These characteristics give rise to the need for transformation into
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27 corresponding derivatives with desirable chromatographic or detection properties10.
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29 Derivatization process is known for many years and is often used for amine compounds. The
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milestones of derivatization is presented in Table 1.
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34 A review of different methods of the derivatization process (at particular stages of
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36 analytical procedures) using common derivatizing reagents is presented here. The application of
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microextraction techniques coupled with derivatization of amines is also discussed. On
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derivatization, the analyte polarity is decreased resulting in an increase in the partition
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43 coefficient, while at the same time, the chemical conversion process allows for an increase in
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45 performance with respect to chromatographic techniques.
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Table 1. Milestones in development of field of application of derivatization in analytical practice
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50 Year Description Ref.
51 1957 The preparation of derivatives from quantities of substances down to one 11
52 milligram reported
53 1961 The trimethylsilyl group introduced for the GLC analysis of amino acids 12
54 1961 Trimethylsilyl ethers for derivatization of steroids reported 13
55 1963 The trimethylsilyl group applied in carbohydrate chemistry 12
56 1963 First C-Derivatization of Amino Acids reported 14
57 1963 Derivatization using hexamethyldisilazane reported 15
58 1964 Derivatization using Chlorotrimethylsilane reported 16
59 1964 Preparation and decarbonylation of acyl derivatives of cyclopentadienyl metal 17
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6 carbonyls reported
7 1966 Derivatization of thiols with trichloroacetyl isocyanate for NMR analysis reported 18
8 1967 Derivatization using bis-trimethylsilvy acetamide reported 19
9 1968 Determination of amino acids present in nanomolar quantities in biological 20
10 samples after its derivatization using GC reported
11 1968 N,O-Bis(trimethylsilyl)trifluoroacetamide introduced 15
12 1969 Derivatization using N-Methyl-N-(trimethylsilyl)trifluoroacetamide reported 21
13 1969 The 9-H-hexadecafluoronanoate and 11-H-eicosafluoroundecanoate 22
14 derivative for electron capture - GC of steroids reported
15 1970 Preparation of volatile derivatives of amino acids on a solid support followed by 23
16 direct injection into the gas chromatography column reported
17 1970 The utilization of dansylation methods for quantitative determination of free 24
18 amino acids reported
19 1970 Preparation of steroid heptafluorobutyrates for gas liquid chromatography 25
20 utilizing vapor phase derivatization reported
21 1973 Fluorescamine first time used as a derivatization reagent for primary amines 26
22 detected by MS
23 1974 Fluorimetric derivatization for pesticide residue analysis reported 27
24 1974 (R)-(+)-trans-chrysanthemoyl chloride for the gas-phase analytical resolution of
25 enantiomeric amines and alcohols introduced 28
26 1976 Derivatization using trimetylsilyimidazole reported 29
27 1977 First handbook of derivatives for chromatography published 30
28 1983 Determination of amino acids with 9-fluorenylmethyl chloroformate and 31
29 reversed-phase high-performance liquid chromatography reported
30 1985 Quantitative HPLC determination of amikacin in pharmaceutical formulations 32
31 using precolumn derivatization first time described
32 1989 Dragendorff reagent introduced 33
33 1997 SPME was coupled with derivatization 34
34 2006 FMOC-Cl was introduced into derivatization of glucosamine sulfate in human 35
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36 2006 SBSE in combination with in situ derivatization 36
37 2006 Liquid phase microextraction coupled with in situ derivatization reported 37
38 2006 Dual derivatization–stir bar sorptive extraction–thermal desorption–gas 38
39 chromatography–mass spectrometry reported
40 2006 Dynamic hollow-fiber liquid-phase microextraction coupled with derivatization 39
reported
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2007 Simultaneous dispersive liquid–liquid microextraction and derivatization 40
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combined with GC-electron-capture detection first time used
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2008 Miniaturized hollow fiber assisted solvent microextraction with in situ 41
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derivatization first time reported
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2010 Dispersive liquid–liquid phase microextraction coupled with derivatization first 42
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time reported
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2011 Ionic liquid-based microwave-assisted dispersive liquid–liquid microextraction 43
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and derivatization of sulfonamides in river water, honey, milk, and animal plasma
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2012 Molecularly imprinted-solid phase extraction combined with simultaneous 44
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derivatization and dispersive liquid–liquid microextraction for selective extraction
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and preconcentration of methamphetamine and ecstasy from urine samples
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followed by gas chromatography first time reported.
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2013 Ultrasound assisted dispersive liquid-liquid microextraction followed by injector 45
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port silylation for rapid determination of quinine in urine by GC-MS first time
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reported.
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2013 One-step headspace dynamic in-syringe liquid phase derivatization–extraction 46
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technique for the determination of aqueous aliphatic amines by liquid
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chromatography with fluorescence detection first time reported.
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2013 Derivatization and dispersive liquid–liquid microextraction based on 47
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6 solidification of floating organic droplet method for analysis of amino acids in
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8 2014 In situ derivatization combined with ultrasound-assisted emulsification 48
9 microextraction followed by GC-MS for determination of non-steroidal anti-
10 inflammatory drugs in surface water first time reported.
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2. IMPROVEMENT OF CHROMATOGRAPHIC PROPERTIES BY ANALYTE
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STRUCTURE CHANGE
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18 The low amounts of amines present in different kind of sample (e.g. ng/g), the complex
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sample matrix, and the need for several isolation steps makes accurate quantification difficult.
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Therefore it is necessary to select an appropriate method of sample preparation for analysis (e.g.
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25 type of extraction), and a final determination technique. One should also take into account the
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27 fact that a large group of amines do not possess structural properties which enable determination
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by means of gas or liquid chromatography. Conversion allows for a significant increase in the
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32 possibilities and scope of application of both techniques, for example, it is possible to decrease
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of GC analysis. This contributes to an increase in the sensitivity and selectivity and therefore, a
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lowering of the detection limit1.
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41 Another pertinent challenge is the compliance of the derivatization process with the rules
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43 of green chemistry49 and green analytical chemistry50, which result from the principles of
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balanced development.
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48 There are many known derivatization techniques for amine compounds, the easiest
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50 division being a chemical conversion based on the analytical procedure stage. This process can
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be carried out in a sample matrix, the measuring device dispenser chamber as well as in or
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55 behind the chromatographic column (in situ, pre-column derivatization, on-column
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57 derivatization and post-column derivatization)51,52 (Figure 1). For example, in the case of post-
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6 column derivatization, an extracted analyte is introduced together with the derivatizing reagent to
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a high temperature dispenser and the conversion is performed rapidly. This method reduces the
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11 loss of analyte since extraction is performed before the derivative is formed51. However, post
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The most frequently used derivatization technique for amine compounds is pre-column
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derivatization, that is, at sample collection or preparation for transport, or directly before analysis
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20 (in situ or in the dispenser of a control-measuring device within a laboratory environment)51.
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Figure 1. Schematic representation of analyte transformation method into derivatives depending
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on the process site53: A) Pre-column derivatization: 1) on SPME fiber; 2) directly in the sample
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taken or during sample-taking stage (in situ); B) In chromatograph dispenser chamber or on
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This procedure simplifies the sample preparation process by injecting the sample/reagent mixture
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34 directly or separately, thus avoiding the need for extra apparatus, e.g. a heater to assist the
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where the sample is introduced into the column and presents different challenges that have to be
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acknowledged). Compared with off-line methods, injection port derivatization shows advantages
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43 in terms of convenience and “green” operability, high reaction efficiency and low cost.
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Another method of derivatization is the direct conversion of the substance within the
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sample at or after the collection stage54. In the determination of amine compounds, in situ
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50 derivatization is often coupled with the extraction process. Among the “green” extraction
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procedures are carried out on:
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57 • a fiber for an SPME device which is used for analyte sampling from a medium and its
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