Urine, Volatile compounds

Novikov, S.N, Daev E.V. Tzapigina R.I. 1985. Influence of urine volatile compounds on generative function in prepubertal male mice, Mus musculus L. Dokl Akad. Nauk SSSR., 281, 1506—1508. (in Russian). 

The kidney is an important organ for the excretion of toxic materials and their metaboHtes, and measurement of these substances in urine may provide a convenient basis for monitoring the exposure of an individual to the parent compound in his or her immediate environment. The Hver has as one of its functions the metaboHsm of foreign compounds some pathways result in detoxification and others in metaboHc activation. Also, the Hver may serve as a route of elimination of toxic materials by excretion in bile. In addition to the Hver (bile) and kidney (urine) as routes of excretion, the lung may act as a route of elimination for volatile compounds. The excretion of materials in sweat, hair, and nails is usually insignificant. 

Novotny, M.V., Soini, H.A., Koyama, S., Wiesler, D., Bruce, K.E. and Penn, D.J. (2007) Chemical identification of MHC-influenced volatile compounds in mouse urine. I Quantitative proportions of major chemosignals. J. Chem. Ecol. 33, 417—434. 

Jemiolo, D., Alberts, J., Sochinski-Wiggins, S., Harvey, S. and Novotny, M. (1985) Behavioural and endocrine responses of female mice to synthetic analogs of volatile compounds in male urine. Anim. Behav. 33, 1114-1118. 

Tarsal, metatarsal, caudal, interdigital and preorbital glandular structures have been described in the black-tailed deer, Odocoileus hemionus columbianus. The tarsal organ received considerable attention from chemists and behavioral scientists during the early years of chemical research on mammalian semiochemicals. The major constituent of the complex mixture of volatile compounds associated with the tarsal hair tuft of this mule deer, (Z)-6-dodecen-4-olide [ 125], was subsequently found to be a mixture of the R and S enantiomers in a ratio of 89 11 respectively [ 126]. It was later found that this compound does not originate in the tarsal structure itself, but that it is extracted from the animal s urine by the tarsal hair tuft, which is specially adapted to extract lipids from urine [127]. 

A mammal may emit many volatile compounds. Humans, for instance, give off hundreds of volatiles, many of them chemically identified (Ellin etal., 1974). The volatiles include many classes of compound such as acids (gerbil), ketones, lactones, sulfides (golden hamster), phenolics (beaver, elephant), acetates (mouse), terpenes (elephant), butyrate esters (tamarins), among others. The human samples mentioned before contained hydrocarbons, unsaturated hydrocarbons, alcohols, acids, ketones, aldehydes, esters, nitriles, aromatics, heterocyclics, sulfur compounds, ethers, and halogenated hydrocarbons. Sulfur compounds are found in carnivores, such as foxes, coyotes, or mustelids. The major volatile compound in urine of female coyotes, Canis latrans, is methyl 3-methylhut-3-enyl sulfide, which accounts for at least 50% of all urinary volatiles (Schultz etal, 1988). 

Despite the distinct advantages of pneumatic nebulizers, ultrasonic nebulizers may alternatively be used, in some instances, with success. In a recent application, a variation of ultrasonic nebulizer called spray nozzle-rotating disk FTIR interface was successfully applied to confirm the presence of methyltestosterone, testosterone, fluoxymesterone, epitestosterone, and estradiol and testosterone cyp-ionate in urine, after solid-phase extraction and reversed-phase LC separation (151). Using a commercial infrared microscopy spectrometer, usable spectra from 5 ng steroid deposits could be readily obtained. To achieve success with this interface, phosphate buffers in the mobile phase were not used because these nonvolatile salts accumulate on the collection disk and their spectra tend to swamp out small mass deposits. Another limitation of the method was that only nonvolatile analytes could be analyzed because volatile compounds simply evaporated off the collection-disk surface prior to scanning. 

Several strains of LAB isolated from wine were tested for their abilities to metabolize ferulic and p-coumaric acids. Cavin et al. (1993) showed that these acids were strongly decarboxylated by growing cultures of Lactobacillus brevis, Lactobacillus plantarum, and Pediococcus when decarboxylation was observed, volatile phenols (4-ethylguaiacol and 4-ethylphenol) were detected, indicating the possibility of reduction of the side chain before or after decarboxylation. Couto et al. (2006) reported L. collinoides as a producer of volatile phenols, although strain specificity concerning this capacity was observed. L. mali, L. sake, L. viridescens, and P. acidi-lactici were also found to be able to produce volatile compounds but they only perform the decarboxylation step. Volatile phenols cause animal taints such as horse sweat, wet animal and urine that are usually attributed to Brettanomyces spoilage. 

Blood and urine Heat biological sample purge-and-trap volatile compounds on Tenax GC adsorbent GC/MS No data No data Barkley et al. 1980... 

Picloram is not readily metabolized and is rapidly excreted unchanged in the urine and feces of treated rats, hollowing a 10 mg kg [ C]picloram intravenous dose, the isotope was cleared biophysical-ly and excreted in the urine. Balance studies in rats indicated that 98.4% of the dose was recovered. Urinary excretion resulted in an 80-84% recovery, fecal excretion resulted in 15% recovery less than 0.5% was recovered in the bile, and virtually no radioactivity was recovered as trapped " C02 or as other volatile compounds. Studies with [ " C]piclo-ram showed that 90% of the compound fed in the diet to dogs was excreted within 48 h in the urine, with small amounts appearing in the feces. 

One of the most commonly used fibers for VOC analysis is coated with a lOO-pm polydimethylsiloxane phase (PDMS) and is available as a unit with a stainless-steel guide rod housed in a hollow septum-piercing needle (Supelco, Bellefonte, PA, USA). The fiber can be withdrawn into the needle for protection during handling and the depth of fiber exposure can be controlled using the adjustable holder. In HS techniques, the needle can be used to pierce the septum of the sample vial and to introduce the fiber into the injection port of the gas chromatograph. In the sample vial, the extraction onto the fiber reaches equilibrium fairly quickly for volatile compounds. Mills and Walker s review includes tabular summaries of HS-SPME-GC methods for the detection of alcohols, drugs, solvents and chemicals in blood and urine. 

B17. Bonnichsen, R., and Linturi, M., Gas chromatographic determination of some volatile compounds in urine. Acta Chem. Scand. 16, 1289-1290 (1962). 

The most important route of excretion for most non-gaseous or non-volatile compounds is through the kidneys into the urine. Other routes are secretion into the bile, expiration via the lungs for volatile and gaseous substances, and secretion into the gastrointestinal tract, or into fluids such as milk, saliva, sweat, tears and semen. 

The methods of analysis for many of the specific metabolites have been reviewed by Aprea et al. (2002). Most of the specific metabolites arc conjugate glucuromides or sulfates thus, enzyme or acid hydrolysis is required to liberate the metabolites. Most of the methods for the analysis of specific metabolites use GC/ECD or GC/MS. The urine sample (after hydrolysis) is extracted with a solvent, such as eiher or toluene, The filtration of urine is performed through a Sep-Pak C18 cartridge followed by extraction of Ihe eluate with solvents. Several derivatizing reagents such a.s BSA lMO-bis(trimethylsilyl)acetamide], I-chloro-3-iodopentane, or MTBSTFA [A -(tertbutyldiniethylsilyl)-Af-methyl trifluo-roacetamide) have been used to convert the metabolites into volatile compounds. 

Harvey, S., Jemiolo, B., and Novomy, M., 1989, Pattern of volatile compounds in dominant and subordinate male mouse urine, / Chem. Ecol. 15 2061-2071. 

Aliquots (500 nl) of urine were sampled by manual SPME prior to GC/MS. The vials used for SPME were steam-cleaned by hot distilled water, rinsed three times with triple-distilled water, and air-dried prior to the addition of urine. Either a reverse-direction insert top, conditioned for several days in a GC oven at 250 °C, or an aluminum foil cover through which the fiber and its holder were inserted was used. Based on the results from Asian female urine (Rasmussen, 2001), 100-pm polydimethylsiloxane (PDMS) SPME fibers were employed. No fibers were immersed rather, they were exposed in the headspace above the liquid sample, which was gently stirred by a tiny magnetic stirring bar. For each sample, the adsorption of volatile compounds on the fiber was conducted first at native pH and at ambient temperature (25 °C), and then heated to 37 °C. For selected duplicate samples, 1 mg/ml of non-specific bacterial protease (Sigma cat. no. P-5147) was added (Poon et al., 1999 Yamazaki et al., 1999). For some of these samples, the pH was adjusted to 4.0, the pH demonstrated to result in release of ligands from urinary albumin (Lazar et al., 2002). Selected samples were also reduced further to pH 1.0. 

Mills, G. A., and Walker, V., 2001, Headspace solid-phase microextraction profiling of volatile compounds in urine application to metabolic investigations, / Chromatogr. B, 753 259-268. 

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