Sleep, Health Outcomes and Body Weight (SHOW) study: a measurement burst design study on sleep and risk factors for obesity in black emerging adults in North Carolina, USA.

INTRODUCTION: Black emerging adults (18-28 years) have the highest risk of short sleep duration and obesity. This increased risk may be partly explained by greater stress levels, which may result from race-related stress (racial discrimination and heightened race-related vigilance) or living in more disadvantaged home and neighbourhood environments. Insufficient sleep may also impact obesity risk via several weight-related mechanisms including energy balance, appetite and food reward, cortisol profiles and hydration status. This paper describes the rationale, design and methods for the Sleep, Health Outcomes and Body Weight (SHOW) study. This study aims to prospectively assess the effects of sleep, race-related stress and home/neighbourhood environments on weight-related mechanisms and obesity markers (body weight, waist circumference and fat mass) in 150 black emerging adults. METHODS AND ANALYSIS: The SHOW study follows a measurement burst design that includes 3, 7-day data collection bursts (baseline, 6-month and 12-month follow-ups). Sleep is measured with three methods: sleep diary, actigraphy and polysomnography. Energy balance over 7 days is based on resting and postprandial energy expenditure measured via indirect calorimetry, physical activity via accelerometry and self-reported and ad libitum energy intake methods. Self-reported methods and blood biomarkers assess fasting and postprandial appetite profiles and a behavioural-choice task measures food reward. Cortisol awakening response and diurnal cortisol profiles over 3 days are assessed via saliva samples and chronic cortisol exposure via a hair sample. Hydration markers are assessed with 24-hour urine collection over 3 days and fasting blood biomarkers. Race-related stress is self-reported over 7 days. Home and neighbourhood environments (via the Windshield Survey) is observer assessed. ETHICS AND DISSEMINATION: Ethics approval was granted by the University of North Carolina at Greensboro's Institutional Review Board. Study findings will be disseminated through peer-reviewed publications, presentations at scientific meetings and reports, briefs/infographics for lay and community audiences.

Determination of structural building blocks in heavy petroleum systems by collision-induced dissociation Fourier transform ion cyclotron resonance mass spectrometry.

Collision-induced dissociation Fourier Transform ion cyclotron resonance mass spectrometry (CID-FTICR MS) was developed to determine structural building blocks in heavy petroleum systems. Model compounds with both single core and multicore configurations were synthesized to study the fragmentation pattern and response factors in the CID reactions. Dealkylation is found to be the most prevalent reaction pathway in the CID. Single core molecules exhibit primarily molecular weight reduction with no change in the total unsaturation of the molecule (or Z-number as in chemical formula C(c)H(2c+Z)N(n)S(s)O(o)VNi). On the other hand, molecules containing more than one aromatic core will decompose into the constituting single cores and consequently exhibit both molecular weight reduction and change in Z-numbers. Biaryl linkage, C(1) linkage, and aromatic sulfide linkage cannot be broken down by CID with lab collision energy up to 50 eV while C(2)+ alkyl linkages can be easily broken. Naphthenic ring-openings were observed in CID, leading to formation of olefinic structures. Heavy petroleum systems, such as vacuum resid (VR) fractions, were characterized by the CID technology. Both single-core and multicore structures were found in VR. The latter is more prevalent in higher aromatic ring classes.

Enrichment, resolution, and identification of nickel porphyrins in petroleum asphaltene by cyclograph separation and atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry.

We report here the first high resolution mass spectrometric evidence of nickel porphyrins in petroleum. A petroleum asphaltene sample is fractionated by a silica-gel cyclograph. Nickel content is enriched by approximately 3 fold in one of the cyclograph fractions. The fraction is subsequently analyzed by atmospheric pressure photoionization (APPI) Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) with an average mass resolving power of over 500 K (M/DeltaM(fwhm)). Similar to vanadyl porphyrins, monocylcoalkano-type (presumed to be deocophylerythro-etioporphyrin DPEP) Ni porphyrins are found to be the most abundant family followed by etio, bicycloalkano-type, and rhodo-monocylcoalkano-type Ni porphyrins. A Z number ranging from -28 to -44 and a carbon number ranging from 26 to 41 were observed. A significant amount of nickel and vanadyl geoporphyrins are in more condensed tetrapyrrolic cores than just chlorophyll-derived DPEP- and etioporphyrins. Ni has a higher etio/DPEP ratio and rhodo-etio/rhodo-DPEP ratio than does VO.

Rapid hydrocarbon analysis using a miniature rectilinear ion trap mass spectrometer.

A miniature ion trap mass analyzer was applied to the analysis of traces of hydrocarbons and simple heteroatomics in the vapor phase and in aqueous solution. Vapors of acetone, acetic acid, acetonitrile, benzene, butanethiol, carbon disulfide, hexane, dichloromethane, naphthalene, toluene and xylenes were detected and quantified using solid sorbent trapping and, in some cases, by passage through a membrane interface. Aqueous solutions of benzene, toluene, xylenes, hexane and a petroleum naphtha distillate were examined using the membrane interface. Sampling, detection and identification of all compounds was completed in times of less than one minute. The gas-phase samples of toluene and benzene were detected at 200 ppt (limit of detection, LOD) for toluene and 600 ppt for benzene. Identification of benzene and xylene in aqueous solutions was readily achieved with LODs of 200 and 400 ppb, respectively. Quantification over a linear dynamic range of two orders of magnitude for the aqueous samples and three orders of magnitude for the vapor-phase samples was demonstrated.

Observation of vanadyl porphyrins and sulfur-containing vanadyl porphyrins in a petroleum asphaltene by atmospheric pressure photonionization Fourier transform ion cyclotron resonance mass spectrometry.

Vanadyl (VO) porphyrins and sulfur-containing vanadyl (VOS) porphyrins of a wide carbon number range (C(26) to C(52)) and Z-number range (-28 to -54) were detected and identified in a petroleum asphaltene by atmospheric pressure photonionization (APPI) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). APPI provides soft ionization of asphaltene molecules (including VO and VOS porphyrins), generating primarily molecular ions (M(+.)). The ultra-high mass resolving power (m/Delta m(FWHM) approximately 500 K) of FTICR-MS enabled resolution and positive identification of elemental formulae for the entire family of VO and VOS porphyrins in a complicated asphaltene matrix. Deocophylerythro-etioporphyrin (DPEP) is found to be the most prevalent structure, followed by etioporphyrins (etio)- and rhodo (benzo)-DPEP. The characteristic Z-distribution of VO porphyrins suggests benzene and naphthene increment in the growth of porphyrin ring structures. Bimodal carbon number distributions of VO porphyrins suggest possible different origins of low and high molecular weight species. To our knowledge, the observation of VOS porphyrins in a petroleum product has not previously been reported. The work is also the first direct identification of the entire vanadyl porphyrin family by ultra-high resolution mass spectrometry without chromatographic separation or demetallation.

Measurement of total acid number (TAN) and TAN boiling point distribution in petroleum products by electrospray ionization mass spectrometry.

We report a new method for rapid measurement of total acid number (TAN) and TAN boiling point (BP) distribution for petroleum crude and products. The technology is based on negative ion electrospray ionization mass spectrometry (ESI-MS) for selective ionization of petroleum acid and quantification of acid structures and molecular weight distributions. A chip-based nanoelectrospray system enables microscale (<200 mg) and higher throughput (20 samples/h) measurement. Naphthenic acid structures were assigned based on nominal masses of a set of predefined acid structures. Stearic acid is used as an internal standard to calibrate ESI-MS response factors for quantification purposes. With the use of structure-property correlations, boiling point distributions of TAN values can be calculated from the composition. The rapid measurement of TAN BP distributions by ESI is demonstrated for a series of high-TAN crudes and distillation cuts. TAN values determined by the technique agree well with those by the titration method. The distributed properties compare favorably with those measured by distillation and measurement of TAN of corresponding cuts.

Separation of C2-naphthalenes by gas chromatography x fourier transform infrared spectroscopy (GC x FT-IR): two-dimensional separation approach.

A two-dimensional separation approach involving gas chromatography (GC) and Fourier transform infrared spectroscopy (FT-IR) is used to separate C2-naphthalene isomers at or near baseline resolution. In addition to GC separation, the FT-IR also plays an important role in the separation, as well as its traditional role of detection and identification. This two-dimensional separation approach for the analysis of a C2-naphthalene isomeric mixture is a good example of separation design based on molecular difference and the characteristics of an analytical instrument. The details of this two-dimensional separation are discussed, along with the advantages and limitations of this approach. While two-(or multiple-)dimensional separations have demonstrated superior capabilities in the characterization of complex, largely unknown mixtures, the development of GCxFT-IR illustrates the applicability of this analytical approach in the separation of simpler but still challenging, mixtures. The GCxFT-IR results have extended this approach toward its application to the analysis of samples of more complicated composition.