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Measurement of gas-liquid partition coefficient and headspace concentration profiles of perfume materials by solid-phase microextraction and capillary gas chromatography-mass spectrometry

An empirical model describing the relationship between the partition coefficients (K) of perfume materials in the solid-phase microextraction (SPME) fiber stationary phase and the Linearly Temperature Programmed Retention Index (LTPRI) is obtained. This is established using a mixture of eleven selected fragrance materials spiked in mineral oil at different concentration levels to simulate liquid laundry detergent matrices. Headspace concentrations of the materials are measured using both static headspace and SPME-gas chromatography analysis. The empirical model is tested by measuring the K values for fourteen perfume materials experimentally. Three of the calculated K values are within 2-19% of the measured K value, and the other eleven calculated K values are within 22-59%. This range of deviation is understandable because a diverse mixture was used to cover most chemical functionalities in order to make the model generally applicable. Better prediction accuracy is expected when a model is established using a specific category of compounds, such as hydrocarbons or aromatics. The use of this method to estimate distribution constants of fragrance materials in liquid matrices is demonstrated. The headspace SPME using the established relationship between the gas-liquid partition coefficient and the LTPRI is applied to measure the headspace concentration of fragrances. It is demonstrated that this approach can be used to monitor the headspace perfume profiles over consumer laundry and cleaning products. This method can provide high sample throughput, reproducibility, simplicity, and accuracy for many applications for screening major fragrance materials over consumer products. The approach demonstrated here can be used to translate headspace SPME results into true static headspace concentration profiles. This translation is critical for obtaining the gas-phase composition by correcting for the inherent differential partitioning of analytes into the fiber stationary phase.

Journal Article↗

Kinetics and mechanism of gas-phase thermolysis using headspace-gas chromatographic analysis.

Headspace gas chromatography is employed in order to study the thermal decomposition reaction of gaseous di-tert-butyl peroxide (DTBP) in the 130 degrees C to 160 degrees C temperature range and in the presence of n-hexane as the internal standard and nitrogen as the carrier gas. The reaction exclusively yields acetone and ethane as products. First-order kinetics are observed, including when the surface-to-volume ratio (S/V) of the Pyrex 20-mL vial employed as the reactor is increased by packing it with silanized glass wool. However, a small increase in the rate constant values is observed at each temperature, which supports a heterogeneous surface process in DTBP decomposition. The rate constant's dependence on the homogeneous unimolecular decomposition reaction corresponds to the O-O bond rupture of the DTBP molecule in a stepwise three-stage mechanism. Thus, the relevant question of the participation of a surface catalytic effect in the DTBP gas-phase thermolysis can easily be assessed through the procedure described in this work. In general, this is advantageous for the rapid investigation of the reaction kinetics of volatile compounds at different temperatures.

Journal Article↗

Spontaneous mutations in gas vesicle genes of Planktothrix spp. affect gas vesicle production and critical pressure.

Wild-type strains of the cyanobacterium Planktothrix rubescens have a cluster of gas vesicle (gvp) genes with repeats of alternating gvpA and gvpC. The gvpC occurs in three length variants, all with the same 3'-sequence, OmegaC. Spontaneous non-buoyant mutants had lost some of the alternating gvpAC copies and their gvpC genes had a novel 3'-end sequence, PsiC; additional gvpC genes terminating in this sequence were also found in the wild-type and representatives of other GV genotypes. Alleles of gvpC terminating in PsiC occurred only at the downstream ends of the gvpAC clusters investigated; all other gvpCs terminated in OmegaC. Mutants of strains with the GV3 genotype produced only 30-50% of the gas vesicles present in the wild-type; their gas vesicles had lower mean critical pressures (0.70-0.78 MPa) than those in the wild-type (1.05-1.10 MPa).

Amino Acid Sequence↗

Contribution of multiple inert gas elimination technique to pulmonary medicine. 1. Principles and information content of the multiple inert gas elimination technique.

This introductory review summarises four different aspects of the multiple inert gas elimination technique (MIGET). Firstly, the historical background that facilitated, in the mid 1970s, the development of the MIGET as a tool to obtain more information about the entire spectrum of VA/Q distribution in the lung by measuring the exchange of six gases of different solubility in trace concentrations. Its principle is based on the observation that the retention (or excretion) of any gas is dependent on the solubility (lambda) of that gas and the VA/Q distribution. A second major aspect is the analysis of the information content and limitations of the technique. During the last 15 years a substantial amount of clinical research using the MIGET has been generated by several groups around the world. The technique has been shown to be adequate in understanding the mechanisms of hypoxaemia in different forms of pulmonary disease and the effects of therapeutic interventions, but also in separately determining the quantitative role of each extrapulmonary factor on systemic arterial PO2 when they change between two conditions of MIGET measurement. This information will be extensively reviewed in the forthcoming articles of this series. Next, the different modalities of the MIGET, practical considerations involved in the measurements and the guidelines for quality control have been indicated. Finally, a section has been devoted to the analysis of available data in healthy subjects under different conditions. The lack of systematic information on the VA/Q distributions of older healthy subjects is emphasised, since it will be required to fully understand the changes brought about by diseases that affect the older population.

Exercise Test↗

Intraoperative gas cisternography and gas dissection in the operative treatment of pituitary tumors. A methodological description.

We have given a methodological description of gas dissection and gas cisternography used during transsphenoidal surgery. 200 consecutive patients with pituitary adenomas or craniopharyngeomas have been operated according to Cushing- Guiot -Hardy's procedure. 68 patients had suprasellar expansions in which gas dissection was used. The operative procedure with technical equipment and staff requirement is reported as well as the combined neurosurgical and neuroradiological techniques.

Adenoma↗

Lateral gas transport in soil adjacent to an old landfill: factors governing gas migration.

Field experiments investigating lateral gas transport in soil adjacent to an old landfill in Denmark during a one-year period were conducted. A significant seasonal variation, with low concentrations of methane and high concentrations of carbon dioxide in the summer, caused by methane oxidation was observed. There was a good correlation between pressure above the barometric pressure and the methane concentration in the soil, indicating that advective flow was the controlling process. This was confirmed by calculations. Diurnal measurement during a drop in barometric pressure showed that lateral migration of landfill gas was a very dynamic system and the concentrations of LFG at a specific place and depth changed dramatically within a very short time. The experiments showed that change in barometric pressure was an important factor affecting gas migration at the Skellingsted landfill in Denmark.

Air Movements↗

Lateral gas transport in soil adjacent to an old landfill: factors governing gas migration.

Field experiments investigating lateral gas transport in soil adjacent to an old landfill in Denmark during a one-year period were conducted. A significant seasonal variation, with low concentrations of methane and high concentrations of carbon dioxide in the summer, caused by methane oxidation was observed. There was a good correlation between pressure above the barometric pressure and the methane concentration in the soil, indicating that advective flow was the controlling process. This was confirmed by calculations. Diurnal measurement during a drop in barometric pressure showed that lateral migration of landfill gas was a very dynamic system and the concentrations of LFG at a specific place and depth changed dramatically within a very short time. The experiments showed that change in barometric pressure was an important factor affecting gas migration at the Skellingsted landfill in Denmark.

Atmospheric Pressure↗

Tracheal gas insufflation and related techniques to introduce gas flow into the trachea.

Over the past 50 years, a variety of techniques have been developed that have in common the insufflation of gas into the central airway to facilitate carbon dioxide (CO2) clearance. These include continuous insufflation of oxygen, transtracheal jet ventilation, high frequency jet ventilation, transtracheal oxygen administration, intratracheal pulmonary ventilation, and tracheal gas insufflation (TGI). Continuous insufflation of oxygen is a technique used to enhance CO2 removal in the presence of apnea. Transtracheal jet ventilation and high frequency jet ventilation promote bulk gas flow into the lungs. Some techniques, such as transtracheal oxygen administration, provide insufflation of oxygen as an adjunct to spontaneous ventilation. However, other techniques, such as TGI, are used as an adjunct to positive pressure ventilation. Intratracheal pulmonary ventilation provides positive pressure ventilation while bypassing the upper airway. Although some of these techniques are promising adjuncts to mechanical ventilation and may help reduce ventilator-associated lung injury, much remains to be learned about their role in the care of patients with acute lung injury.

Equipment Design↗

Controlling self-incompatibility by CO2 gas treatment in Brassica campestris: structural alteration of papillae cell and differential gene expression by increased CO2 gas.

Self-imcompatibility is a controlling genetic mechanism to prevent self-pollination for Chinese cabbage (Brassica campestris), one of the major vegetable crops in Korea. To maintain inbred lines of the crop plant, a method in that high CO2 gas is treated to the pistils to overcome the self-incompatibility and thereby self-pollens can successfully make germination and fertilization has been widely used in seed companies. Despite the common utilization of this method, any molecular and cellular studies on how the self-incompatibility is removed from the Chinese cabbage plant have not been done. In this study, we show that the increased CO2 gas causes a structural alteration of the papillae cell and thereby the self-incompatibility is removed from the Chinese cabbage plant, allowing the self-pollens to germinate and penetrate the papillae cell. Also, gene expression in the pistil treated with CO2 gas was studied by DD/RT-PCR and reverse northern hybridization experiments. The results suggest that the failure in self-incompatible reaction resulted not only from the structural alteration of the papillae cell but also from change in the pistil component production that is either positively or negatively regulated by the environmental stimulation.

Blotting, Northern↗

A system for studying the gas exchange of whole plants at subambient total gas pressures.

A whole-plant gas exchange system that has been designed and constructed to study the feasibility of growing plants at subambient total gas pressures is described. This system will allow for the study of whole-plant gas exchange over the entire life cycle of a plant. The system also will allow for the regulation of atmospheric composition by providing control over the amount of nitrogen, oxygen, and carbon dioxide in a chamber atmosphere. The chamber's environmental performance is discussed in relation to selected design requirements. This system is a major technological advance over other systems used to study low-pressure effects on plant growth.

Air Conditioning↗

[High frequency jet ventilation in heated gas saturated in water vapor without a reserve of medical gas under pressure. An original method].

A prototype of high frequency jet ventilator is compared with a classic device: Gambro Soxijet ventilator. The advantages of the prototype are: no need of pressured medical gas; warming and saturated moisture of the gas. A powerful compressor (2 M3.H-1 flow--3 bar pressure) draws up the moistened and warmed gases and injects them into a double pneumatic capacity. The first capacity is pressure limited by a relief valve (3 bar). Exhausted gases flow back to the pump. A miniature pressure regulator, placed between the two capacities, rules the driving pressure. Gas mixture is injected through a solenoid valve controlled by an electronic twin-timer. Results of both devices are similar. However, our prototype seems to be very convenient for developing countries where medical gases under high pressure are not often available.

Developing Countries↗

Placental gas exchange in the guinea-pig: fetal blood gas tensions following the reduction of maternal oxygen capacity with carbon monoxide.

The effect of CO hypoxia on the placental exchange of respiratory gases was studied in anaesthetized pregnant guinea-pigs near term. Fetal PO2 and PCO2 were measured by mass spectrometry from a blood gas catheter in the right atrium. Administration of 5 ml CO over 65 s reduced maternal oxygen capacity by 26%. There was a rapid fall in fetal arterial PO2 and a more gradual rise in fetal PCO2. It was shown in separate experiments that the carboxyhaemoglobin content of fetal blood did not alter greatly in the first few min. after CO administration, which is the interval within which fetal PO2 was seen to fall. The alteration in fetal gas tensions can therefore be ascribed to the increased oxygen affinity and reduced oxygen capacity occasioned by the presence of carboxyhaemoglobin in the maternal blood. The alteration in placental oxygen transfer was calculated from the experimental findings, using a mathematical model of placental gas exchange in the guinea-pig. The total reduction in the oxygen transfer was 32% of the initial value. It was calculated that the reduction in maternal oxygen capacity was responsible for about two-thirds of this decrease, the remainder being due to the increased oxygen affinity of maternal blood.

Acid-Base Equilibrium↗

[Gas exchange and transport in the body during acute anemia correction by modified hemoglobin solution or attributed to inhalation of a hyperoxic gas mixture].

Total and specific characteristics of changes in gas exchange and transport, tissue oxygenation, circulatory and respiratory compensatory reactions were examined in three groups of necrotized Wistar rats during acute anemia correction by two methods, replacement of red cell mass loss with modified hemoglobin solution (Hb 4.4 g/dl, P50 21.5 mm Hg) or respiration with a hyperoxic mixture (90% of oxygen in nitrogen). In control animals anemia was induced with blood replacement with 6% albumin solution during atmospheric air inhalation. The studied methods for anemia correction were found to increase oxygen levels in arterial blood and similarly effective in total gas exchange maintenance; however the mechanisms of oxygen delivery from arterial blood to tissues being quite different, use of hemoglobin solution was associated with a number of adverse features in gas transport system, acid-base balance, reactions of minute volumes of circulation and respiration which were caused by changed oxygen-binding characteristics of modified hemoglobin and the presence of high concentrations of free hemoglobin in blood plasma.

Acute Disease↗

The determination of total and unbound midazolam in human plasma. A comparison of high performance liquid chromatography, gas chromatography and gas chromatography/mass spectrometry.

Midazolam concentrations in patients' plasma was determined after extraction with high performance liquid chromatography (HPLC), gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). GC was selected for routine plasma assays in terms of selectivity, simplicity, precision, accuracy and sensitivity (0.02 microgram/mL); HPLC analysis was less sensitive (0.1 microgram/mL) than GC; GC/MS was used for analysis validation. Plasma protein binding of midazolam was determined by GC in patients' plasma after in vitro incubation with midazolam, ultrafiltration and extraction; 5% of the drug was unbound to plasma proteins. Midazolam distribution in lipoprotein fractions separated by ultracentrifugation of plasma obtained from patients on prolonged midazolam treatment was also assayed by GC.

Blood Proteins↗

Automated profiling of urinary organic acids by dual-column gas chromatography and gas chromatography/mass spectrometry.

A multi-stage screening and identification scheme for the diagnosis of inborn errors in amino acid, fatty acid, carbohydrate and intermediary metabolism is described. The method is based on a computerized analysis of data obtained with dual-column gas chromatography/FID (GC/FID) and gas chromatography/mass spectrometry (GC/MS) profiling of urinary organic acids. It involves: (1) isolation of the compounds by solvent or solid-phase extraction; (2) conversion into trimethylsilyl (TMS) or TMS-oxime derivatives; (3) GC/FID analysis on SE-52 and OV-1701 capillary columns; (4) tentative identification by comparing the methylene unit (MU) values on both columns with a user-built library of reference compounds; (5) quantitative evaluation of the excretion profile; and (6) analysis by GC/MS of samples with an abnormal profile using an automated peak identification programme.

Acids↗

Identification of character-impact odorants in coriander and wild coriander leaves using gas chromatography-olfactometry (GCO) and comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC x GC-TOFMS).

The essential oil of coriander leaves (Coriandrum sativum) and wild coriander leaves (Eryngium foetidum) grown in Fiji was obtained by steam distillation. The aroma profiles were characterised using gas chromatography-olfactometry (GCO) and CharmAnalysis. The character-impact odorants were identified using comprehensive two-dimensional gas chromatography (GC x GC) combined with time-of-flight mass spectrometry (TOFMS). During GCO analysis, the co-elution of E-2-alkenals and E-2-alken-1-ols resulted in the perception of 'odour-clusters'. The most important odorants in C. sativum were found to be Z-2-decenal, a co-eluting odour-cluster (E-2-dodecenal, E-2-dodecen-1-ol, and 1-dodecanol), beta-ionone, eugenol, and E-2-decenal. E-2-decen-1-ol was the most abundant compound in C. sativum (26.0% TIC) but only contributed 0.39% of the total odour activity. The most abundant compound in E. foetidum was E-2-dodecenal (63.5% TIC), which also contributed the most odour activity (52.9%). Other important odorants were either eugenol or a trimethylbenzaldehyde isomer, beta-ionone, Z-4-dodecenal, dodecanal, and E-2-tetradecenal. GC x GC-TOFMS allowed the identification of 42 and 20 compounds not previously reported in the literature for C. sativum and E. foetidum, respectively. In particular, beta-ionone was determined to be an important odorant in both samples but could not be identified with GC-qMS.

Chromatography, Gas↗

The use of gas chromatography and gas chromatography-mass spectrometry for the characterization of permethylated oligosaccharides with molecular mass up to 2300.

Gas chromatography and gas chromatography-mass spectrometry were adapted for the analysis of large permethylated oligosaccharides of different types. Permethylated isomaltooligosaccharides with up to 11 sugar residues and a mass of 2291 Da and two branched blood group H-type decasaccharides derived from the corresponding glycosphingolipids with masses of 2150 Da were successfully analyzed. The capillary columns used have extremely good resolution exemplified by the separation of the two decasaccharides which only differed by one internal linkage position and by the separation of four isomeric tetrasaccharides. The combined information of retention times and mass spectra gave detailed information of 22 neutral oligosaccharides from porcine intestinal mucin and the approach thus allow quick screening of O-linked-type glycans. The procedure for permethylation of oligosaccharides using solid NaOH has been investigated and adapted for structures having a glucose alditol as in reduced oligosaccharides derived from milk and glycosphingolipids.

Animals↗