Breath testing for intra-abdominal infection: appendicitis, a preliminary study.

In the current pilot study we aimed to determine whether breath analysis could be used to help recognise intra-abdominal infection, using acute appendicitis as an exemplar condition. Our study included 53 patients (aged 18-88 years) divided into three groups: appendix group, 26 (13 male) patients suffering from acute appendicitis; control group 20 (seven male) patients undergoing elective abdominal surgery; normal group, seven patients who were clinically diagnosed with appendicitis, but whose appendix was normal on histological examination. Samples of breath were analysed using ion molecule reaction mass spectroscopy measuring the concentration of volatile compounds (VCs) with molecular masses 27-123. Intraperitoneal gas samples were collected from a subset of 23 patients (nine diagnosed with acute appendicitis). Statistically significant differences in the concentration of VCs in breath were found between the three groups. Acetone, isopropanol, propanol, butyric acid, and further unassigned VCs with molecular mass/charge ratio (m/z) 56, 61 and 87 were all identified with significant endogenous contributions. Principle component analysis was able to separate the control and appendicitis groups for seven variables: m/z = 56, 58, 59, 60, 61, 87 and 88. Comparing breath and intraperitoneal samples showed significant relationships for acetone and the VC with m/z = 61. Our data suggest that it may be possible to help diagnose acute appendicitis by breath analysis; however, factors such as length of starvation remain to be properly accounted for and the management or mitigation of background levels needs to be properly addressed, and larger studies relating breath VCs to the causative organisms may help to highlight the relative importance of individual VCs.

Measurement of breath acetone in patients referred for an oral glucose tolerance test.

Breath acetone concentrations were measured in 141 subjects (aged 19-91 years, mean = 59.11 years, standard deviation = 12.99 years), male and female, undergoing an oral glucose tolerance test (OGTT), having been referred to clinic on suspicion of type 2 diabetes. Breath samples were measured using an ion-molecule-reaction mass spectrometer, at the commencement of the OGTT, and after 1 and 2 h. Subjects were asked to observe the normal routine before and during the OGTT, which includes an overnight fast and ingestion of 75 g glucose at the beginning of the routine. Several groups of diagnosis were identified: type 2 diabetes mellitus positive (T2DM), n = 22; impaired glucose intolerance (IGT), n = 33; impaired fasting glucose, n = 14; and reactive hypoglycaemia, n = 5. The subjects with no diagnosis (i.e. normoglycaemia) were used as a control group, n = 67. Distributions of breath acetone are presented for the different groups. There was no evidence of a direct relationship between blood glucose (BG) and acetone measurements at any time during the study (0 h: p = 0.4482; 1 h: p = 0.6854; and 2 h: p = 0.1858). Nor were there significant differences between the measurements of breath acetone for the control group and the T2DM group (0 h: p = 0.1759; 1 h: p = 0.4521; and 2 h: p = 0.7343). However, the ratio of breath acetone at 1 h to the initial breath acetone was found to be significantly different for the T2DM group compared to both the control and IGT groups (p = 0.0189 and 0.011, respectively). The T2DM group was also found to be different in terms of ratio of breath acetone after 1 h to that at 2 h during the OGTT. And was distinctive in that it showed a significant dependence upon the level of BG at 2 h (p = 0.0146). We conclude that single measurements of the concentrations of breath acetone cannot be used as a potential screening diagnostic for T2DM diabetes in this cohort, but monitoring the evolution of breath acetone could open a non-invasive window to aid in the diagnosis of metabolic conditions.

Laser spectroscopy on volatile sulfur compounds: possibilities for breath analysis.

There is an emerging interest in the detection of volatile sulfur compounds (VSCs) in the breath environment, given their biological relevance as potential signatures of several pathological conditions. Particularly, laser-based spectroscopic sensors are candidates for conducting accurate breath diagnostics in clinical settings. With these aims in mind, the current status of VSC sensing via laser absorption spectroscopy is reviewed in this paper. Attention has been focused on the most promising exhaled markers of pathological conditions, namely hydrogen sulfide, carbonyl sulfide, methanethiol, carbon disulfide and dimethyl sulfide. Details of the most relevant spectroscopic studies conducted on such molecules are presented, together with suggestions on the future direction of this challenging analytical field.

Trace species detection in the near infrared using Fourier transform broadband cavity enhanced absorption spectroscopy: initial studies on potential breath analytes.

Cavity enhanced absorption measurements have been made of several species that absorb light between 1.5 and 1.7 µm using both a supercontinuum source and superluminescent light emitting diodes. A system based upon an optical enhancement cavity of relatively high finesse, consisting of mirrors of reflectivity ∼99.98%, and a Fourier transform spectrometer, is demonstrated. Spectra are recorded of isoprene, butadiene, acetone and methane, highlighting problems with spectral interference and unambiguous concentration determinations. Initial results are presented of acetone within a breath-like matrix indicating ppm precision at <∼10 ppm acetone levels. Instrument sensitivities are sufficiently enhanced to enable the detection of atmospheric levels of methane. Higher detection sensitivities are achieved using the supercontinuum source, with a minimum detectable absorption coefficient of ∼4 × 10(-9) cm(-1) reported within a 4 min acquisition time. Finally, two superluminescent light emitting diodes are coupled together to increase the wavelength coverage, and measurements are made simultaneously on acetylene, CO(2), and butadiene. The absorption cross-sections for acetone and isoprene have been measured with an instrumental resolution of 4 cm(-1) and are found to be 1.3 ± 0.1 × 10(-21) cm(2) at a wavelength of 1671.9 nm and 3.6 ± 0.2 × 10(-21) cm(2) at 1624.7 nm, respectively.

Near-infrared broad-band cavity enhanced absorption spectroscopy using a superluminescent light emitting diode.

A fibre coupled near-infrared superluminescent light emitting diode that emits approximately 10 mW of radiation between 1.62 and 1.7 microm is employed in combination with a broad-band cavity enhanced spectrometer consisting of a linear optical cavity with mirrors of reflectivity approximately 99.98% and either a dispersive near-infrared spectrometer or a Fourier transform interferometer. Results are presented on the absorption of 1,3-butadiene, and sensitivities are achieved of 6.1 x 10(-8) cm(-1) using the dispersive spectrometer in combination with phase-sensitive detection, and 1.5 x 10(-8) cm(-1) using the Fourier transform interferometer (expressed as a minimum detectable absorption coefficient) over several minutes of acquisition time.

Characterization of an external cavity diode laser based ring cavity NICE-OHMS system.

The performance of an external cavity diode laser based noise immune cavity enhanced optical heterodyne molecular spectrometer is presented. To reduce the noise on the signal a ring cavity and a circuit to remove residual amplitude modulation on the pre-cavity laser radiation was implemented. We demonstrate a sensitivity of 4 x 10(-11) cm(-1) Hz(-1/2) using a cavity with a finesse of 2600 on a Doppler-broadened transition of CH(4) at 6610.063 cm(-1).

A chemometric study on human breath mass spectra for biomarker identification in cystic fibrosis.

Alveolar breath samples from a small case-control study population have been collected and measured via ion-molecule reaction mass spectrometry, and a constructive statistical approach to the identification of volatile biomarkers has been formulated by applying multivariate statistical methods on the mass spectra. The nature of the data is such that the number of variables largely exceeds the observations, representing a typical experimental scenario when breath analysis is conducted using mass spectrometry. Principal components analysis has been performed on the high dimensional dataset of molecular abundances, providing evidence of case separation and reducing the number of functional discriminators by almost 90%. Afterwards, a deductive approach based on a binary regression was conducted on the reduced dataset, providing an entirely reliable case discrimination model exclusively depending on the concentrations in the breath mixture of 3 out of a total of 97 metabolites.

Methyl iodide photodissociation at 193 nm: The I(2P(1/2)) quantum yield.

Methyl iodide photolysis at 193 nm has been studied through probing the I((2)P(1/2)-(2)P(3/2)) transition in the atomic iodine photofragment using diode laser spectroscopy. The I((2)P(1/2)) quantum yield has been determined through two different diode laser techniques and then compared. Frequency-modulated diode laser based absorption spectroscopy was used to extract nascent Doppler lineshapes from which an I((2)P(1/2)) quantum yield of unity is inferred. However when diode laser gain/absorption measurements were made, an I((2)P(1/2)) quantum yield of 0.68 ± 0.04 was found. The reason for this discrepancy is shown to lie in the diode laser gain/absorption method. Molecular iodine is found to be formed during the experiment via atomic iodine recombination and then in turn dissociates to produce both I((2)P(1/2)) and I((2)P(3/2)), thus distorting the returned quantum yield. This conclusion is supported both by the reduction of the I((2)P(1/2)) quantum yield with number of photolysis laser shots when measured using this technique and by the presence of fluoresence which is shown to have excited-state lifetimes and quenching rates that are consistent with those previously measured for the D and D' states of molecular iodine.

266 nm photolysis of CF3I and C2F5I studied by diode laser gain FM spectroscopy.

Frequency modulated diode laser based absorption at 1.315 microm has been used to measure the Doppler lineshapes of the I((2)P(1/2)-(2)P(3/2)) transition in atomic iodine produced from the 266 nm photolysis of both CF(3)I and C(2)F(5)I. Wavelength resolved laser gain is seen following photolysis as excited iodine atoms ((2)P(1/2)) are produced with a quantum yield close to unity from photolysis of both parent molecules. Time resolved measurements were made and the nascent speed distribution and translational anisotropy parameter, beta were determined. Mean atomic speeds of 800 and 850 ms(-1), which correspond to 83 and 68% of the maximum possible kinetic energy release into the iodine photofragment, were determined for photolysis of CF(3)I and C(2)F(5)I, respectively. The nascent translational anisotropy parameter was found to be beta = 1.77 +/- 0.05 for CF(3)I and beta = 1.69 +/- 0.05 for C(2)F(5)I. These values are explicable in terms of parent rotational motion and non-adiabatic processes in the exit channel.