Isotope ratio monitoring gas chromatography/Mass spectrometry of D/H by high temperature conversion isotope ratio mass spectrometry

Of all the elements, hydrogen has the largest naturally occurring variations in the ratio of its stable isotopes (D/H). It is for this reason that there has been a strong desire to add hydrogen to the list of elements amenable to isotope ratio monitoring gas chromatography/mass spectrometry (irm-GC/MS). In irm-GC/MS the sample is entrained in helium as the carrier gas, which is also ionized and separated in the isotope ratio mass spectrometer (IRMS). Because of the low abundance of deuterium in nature, precise and accurate on-line monitoring of D/H ratios with an IRMS requires that low energy helium ions be kept out of the m/z 3 collector, which requires the use of an energy filter. A clean mass 3 (HD(+.)) signal which is independent of a large helium load in the electron impact ion source is essential in order to reach the sensitivity required for D/H analysis of capillary GC peaks. A new IRMS system, the DELTA(plus)XL(trade mark), has been designed for high precision, high accuracy measurements of transient signals of hydrogen gas. It incorporates a retardation lens integrated into the m/z 3 Faraday cup collector. Following GC separation, the hydrogen bound in organic compounds must be quantitatively converted into H(2) gas prior to analysis in the IRMS. Quantitative conversion is achieved by high temperature conversion (TC) at temperatures >1400 degrees C. Measurements of D/H ratios of individual organic compounds in complicated natural mixtures can now be made to a precision of 2 per thousand (delta notation) or, better, with typical sample amounts of approximately 200 ng per compound. Initial applications have focused on compounds of interest to petroleum research (biomarkers and natural gas components), food and flavor control (vanillin and ethanol), and metabolic studies (fatty acids and steroids). Copyright 1999 John Wiley & Sons, Ltd.     

Metabolic profiling of major vitamin D metabolites using Diels–Alder derivatization and ultra-performance liquid chromatography–tandem mass spectrometry

Biologically active forms of vitamin D are important analytical targets in both research and clinical practice. The current technology is such that each of the vitamin D metabolites is usually analyzed by individual assay. However, current LC-MS technologies allow the simultaneous metabolic profiling of entire biochemical pathways. The impediment to the metabolic profiling of vitamin D metabolites is the low level of 1α,25-dihydroxyvitamin D₃ in human serum (15–60 pg/mL). Here, we demonstrate that liquid–liquid or solid-phase extraction of vitamin D metabolites in combination with Diels–Alder derivatization with the commercially available reagent 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) followed by ultra-performance liquid chromatography (UPLC)–electrospray/tandem mass spectrometry analysis provides rapid and simultaneous quantification of 1α,25-dihydroxyvitamin D₃, 1α,25-dihydroxyvitamin D₂, 24R,25-dihydroxyvitamin D₃, 25-hydroxyvitamin D₃ and 25-hydroxyvitamin D₂ in 0.5 mL human serum at a lower limit of quantification of 25 pg/mL. Precision ranged from 1.6–4.8 % and 5–16 % for 25-hydroxyvitamin D₃ and 1α,25-dihydroxyvitamin D₃, respectively, using solid-phase extraction. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

How does cold constrain life cycles of terrestrial plants and animals?

Short summer seasons with low thermal energy input characterise polar ecosystems. Climatic variables and physical isolation of terrestrial habitats act as selective filters which must be passed to allow colonisation, establishment and survival in these extreme environments. Life history studies of the terrestrial biota of such ecosystems give little evidence of adaptive responses to low temperatures having evolved in situ, even though behavioural, ecophysiological and biochemical features allowing tolerance of the likely extremes are well-developed. Observed life history strategies are often consistent with the general predictions of adversity (A) or stress (S) selection. However, biota successful in these extreme environments may be better-grouped by the lack of particular life history features, rather than common possession.     

Sequential Nucleophilic Substitution: A Powerful Strategy for the Solid-Phase Production of Diverse Compound Libraries

Polyfunctionalized, unprotected reagents (e.g. amines and thiols) can be used in the production of highly diverse compound libraries by performing sequential nucleophilic substitutions on support-bound polyelectrophiles (see scheme). The procedure reported here enables the efficient preparation of new beta-alanine derivatives which are suitable for lead discovery. E*=polyelectrophile, *=solid support.