This paper comprises an updated version of the 2014 review which reported 1846 volatile organic compounds (VOCs) identified from healthy humans. In total over 900 additional VOCs have been reported since the 2014 review and the VOCs from semen have been added. The numbers of VOCs found in breath and the other bodily fluids are: blood 379, breath 1488, faeces 443, milk 290, saliva 549, semen 196, skin 623 and urine 444. Compounds were assigned CAS registry numbers and named according to a common convention where possible. The compounds have been included in a single table with the source reference(s) for each VOC, an update on our 2014 paper. VOCs have also been grouped into tables according to their chemical class or functionality to permit easy comparison. Careful use of the database is needed, as a number of the identified VOCs only have level 2—putative assignment, and only a small fraction of the reported VOCs have been validated by standards. Some clear differences are observed, for instance, a lack of esters in urine with a high number in faeces and breath. However, the lack of compounds from matrices such a semen and milk compared to breath for example could be due to the techniques used or reflect the intensity of effort e.g. there are few publications on VOCs from milk and semen compared to a large number for breath. The large number of volatiles reported from skin is partly due to the methodologies used, e.g. by collecting skin sebum (with dissolved VOCs and semi VOCs) onto glass beads or cotton pads and then heating to a high temperature to desorb VOCs. All compounds have been included as reported (unless there was a clear discrepancy between name and chemical structure), but there may be some mistaken assignations arising from the original publications, particularly for isomers. It is the authors’ intention that this work will not only be a useful database of VOCs listed in the literature but will stimulate further study of VOCs from healthy individuals; for example more work is required to confirm the identification of these VOCs adhering to the principles outlined in the metabolomics standards initiative. Establishing a list of volatiles emanating from healthy individuals and increased understanding of VOC metabolic pathways is an important step for differentiating between diseases using VOCs.
This paper describes the design, development and characterisation of an electrochemical biosensor for the measurement of linoleic and α-linolenic acid, as representative free polyunsaturated fatty acids (PUFAs), that may be implicated in food safety and food quality. Initial cyclic voltammetric studies were performed with solutions that contained enzyme-generated hydroperoxides of the two PUFAs. These were examined with plain screen-printed carbon electrodes (SPCEs) and screen-printed carbon electrodes containing the electrocatalyst cobalt phthalocyanine (CoPC). The electrocatalytic oxidation peaks obtained with the latter occurred at potentials about 300 mV lower than the those obtained by direct oxidation with the plain SPCEs and were better defined; as these attributes would lead to better selectivity and sensitivity for fatty acid determinations, the CoPC-SPCEs were used in the fabrication of amperometric biosensors. The enzyme lipoxygenase (LOX) was immobilised on the surface of these devices using the crosslinking agent glutaraldehyde. These biosensors were optimised for the measurement of linoleic and α-linolenic acid using amperometry in stirred solution; the optimum conditions were deduced by studying the effect of enzyme loading, pH and temperature on the amperometric responses. These responses were examined over the concentration range 2.0 to 20 µM and the results indicated that the following conditions were optimal: LOX loading 15 units; pH 8.0; temperature 37 °C. Low concentration calibration studies were performed with the two PUFAs and it was shown that the steady state currents were linear between 0.2 and 10 µM for linoleic acid and 0.2 and 10 µM for α-linolenic acid; the detection limits were 24 and 100 nM, respectively. The precision (coefficient of variation, n = 6) was 5.3% for α-linoleic acid and 3.3% for linoleic acid, which were calculated from the steady state current following additions (n = 6) of 0.2 µM PUFA. These results demonstrate that the novel amperometric biosensor holds promise for determining whether foods contain acceptable levels of free fatty acids.
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