A literature survey of all volatiles from healthy human breath and bodily fluids: the human volatilome.

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.

An Electrocatalytic Screen-Printed Amperometric Sensor for the Selective Measurement of Thiamine (Vitamin B1) in Food Supplements.

An electrocatalytic screen-printed sensor has been investigated for the measurement of the biologically important biomolecule vitamin B1 (thiamine) for the first time in food supplements. Under basic conditions, the vitamin was converted to its electrochemically active thiolate anion species. It was shown that an electrocatalytic oxidation reaction occurred with the screen-printed carbon electrode containing the mediator cobalt phthalocyanine (CoPC-SPCE). This had the advantage of producing an analytical response current at an operating potential of 0 V vs. Ag/AgCl compared to +0.34 V obtained with plain SPCEs. This resulted in improved selectivity and limit of detection. Detailed studies on the underlying mechanism occurring with the sensor are reported in this paper. A linear response was obtained between 0.1 and 20 µg mL-1, which was suitable for the quantification of the vitamin in two commercial products containing vitamin B1. The mean recovery for a multivitamin tablet with a declared content of 5 mg was 101% (coefficient of variation (CV) of 9.6%). A multivitamin drink, which had a much lower concentration of vitamin B1 (0.22 mg/100 mL), gave a mean recovery of 93.3% (CV 7.2%). These results indicate that our sensor holds promise for quality control of food supplements and other food types.

Sniffing out resistance - Rapid identification of urinary tract infection-causing bacteria and their antibiotic susceptibility using volatile metabolite profiles.

Antibiotic resistance is set to be an unprecedented threat to modern medicine. 'Sniffing' bacteria potentially offers a rapid way to determine susceptibility. A successful proof-of-principle study is described, using thermal desorption-gas chromatography-mass spectrometry (TDGCMS) to 'smell' cephalexin and ciprofloxacin resistant and sensitive Urinary Tract Infection (UTI)-causing bacteria. 578 peaks at unique retention times were detected from 86 chromatograms of 18 bacterial isolates (E. coli, K. pneumoniae and P. aeruginosa). The isolates were grown with and without the presence of antibiotic. Chi-square analysis found 9 compounds that differed significantly between cephalexin sensitive and resistant isolates, and 22 compounds that differed significantly between ciprofloxacin sensitive and resistant isolates, at p ≤ 0.05. When antibiotic was added to the media, more differences were found in the cephalexin group, attributed to lysis, but not in the ciprofloxacin group. Further work with large sample sizes will potentially enable the development of diagnostic algorithms using presence/absence of particular compounds of interest.

Gas Chromatography Mass Spectrometry (GC-MS) Quantification of Metabolites in Stool Using 13C Labelled Compounds.

It has become increasingly important to qualitatively and quantitatively assess the volatile metabolites in a range of bodily fluids for use in monitoring health. There has been relatively little work on the quantitative analysis of compounds, particularly with respect to the effects of ethnicity or geographic location. A novel method for the quantification of compounds in stool using 13C labelled compounds as internal standards is presented. Using thermal desorption gas chromatography mass spectrometry, stool samples from 38 healthy volunteers were analysed. The 13C labelled compounds, acetone, ethyl butanoate, ethanoic acid, butanoic acid, 3-methylbutanoic acid, and indole, were added as internal standards. This process mimics the solubility characteristics of the compounds and thus the method was able to quantify the compounds within the solid stool. In total, 15 compounds were quantified: Dimethyl sulphide (26⁻25,626 ng/g), acetone (442⁻3006 ng/g), ethyl butanoate (39⁻2468 ng/g), ethyl 2-methylbutanoate (0.3⁻180 ng/g), dimethyl disulphide (35⁻1303 ng/g), 1-octen-3-one (12 ng/g), dimethyl trisulphide (10⁻410 ng/g), 1-octen-3-ol (0.4⁻58 ng/g), ethanoic acid (672⁻12,963 ng/g), butanoic acid (2493⁻11,553 ng/g), 3-methylbutanoic acid (64⁻8262 ng/g), pentanoic acid (88⁻21,886 ng/g), indole (290⁻5477 ng/g), and 3-methyl indole (37⁻3483 ng/g). Moreover, by altering the pH of the stool to pH 13 in conjunction with the addition of 13C trimethylamine, the method was successful in detecting and quantifying trimethylamine for the first time in stool samples (range 40⁻5312 ng/g). Statistical analysis revealed that samples from U.K. origin had five significantly different compounds (ethyl butanoate, 1-octen-3-ol, ethanoic acid, butanoic acid, pentanoic acid, and indole) from those of South American origin. However, there were no significant differences between vegetarian and omnivore samples. These findings are supported by pre-existing literature evidence. Moreover, we have tentatively identified 12 compounds previously not reported as having been found in stool.