Determination of the chemical environment of sulphur in petroleum asphaltenes by X-ray absorption spectroscopy

Sulphur K-edge X-ray absorption spectra are analysed for a diverse series of petroleum asphaltenes. The spectra of the asphaltenes are interpreted by fitting with a linear superposition of model compound spectra. This analysis procedure is shown to work quite well in a stringent test case. The reduced forms of sulphur, thiophenes and sulphides dominate in all of the asphaltenes. Generally, the sulphoxide group is the most dominant form of the oxidized sulphur. Comparison of the X-ray data with the elemental composition of the asphaltenes shows that the sulphur and oxygen are preferentially bonded to each other. The inverse dependence of the oxygen-sulphur correlation with the fraction of sulphur which is sulphide suggests that oxidation of sulphur occurs preferentially at the sulphide group.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/30280/1/0000681.pd

Combining biomarker and bulk compositional gradient analysis to assess reservoir connectivity

Author Posting. © The Author(s), 2010. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Organic Geochemistry 41 (2010): 812-821, doi:10.1016/j.orggeochem.2010.05.003.Hydraulic connectivity of petroleum reservoirs represents one of the biggest uncertainties for both oil production and petroleum system studies. Here, a geochemical analysis involving bulk and detailed measures of crude oil composition is shown to constrain connectivity more tightly than is possible with conventional methods. Three crude oils collected from different depths in a single well exhibit large gradients in viscosity, density, and asphaltene content. Crude oil samples are collected with a wireline sampling tool providing samples from well‐defined locations and relatively free of contamination by drilling fluids; the known provenance of these samples minimizes uncertainties in the subsequent analysis. The detailed chemical composition of almost the entire crude oil is determined by use of comprehensive two‐dimensional gas chromatography (GC×GC) to interrogate the nonpolar fraction and negative ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT‐ICR MS) to interrogate the polar fraction. The simultaneous presence of 25‐ norhopanes and mildly altered normal and isoprenoid alkanes is detected, suggesting that the reservoir has experienced multiple charges and contains a mixture of oils biodegraded to different extents. The gradient in asphaltene concentration is explained by an equilibrium model considering only gravitational segregation of asphaltene nanoaggregates; this grading can be responsible for the observed variation in viscosity. Combining these analyses yields a consistent picture of a connected reservoir in which the observed viscosity variation originates from gravitational segregation of asphaltene nanoaggregates in a crude oil with high asphaltene concentration resulting from multiple charges, including one charge that suffered severe biodegradation. Observation of these gradients having appropriate magnitudes suggests good reservoir connectivity with greater confidence than is possible with traditional techniques alone.The mass spectrometry work was supported by the NSF Division of Materials Research through DMR‐06‐54118, and the State of Florida

Integrating comprehensive two-dimensional gas chromatography and downhole fluid analysis to validate a spill-fill sequence of reservoirs with variations of biodegradation, water washing and thermal maturity

Author Posting. © The Author(s), 2016. This is the author's version of the work. It is posted here for personal use, not for redistribution. The definitive version was published in Fuel 191 (2017): 538-554, doi:10.1016/j.fuel.2016.11.081.Optimization of crude oil production depends heavily on crude oil composition and its variation within individual reservoirs and across multiple reservoirs. In particular, asphaltene content has an enormous impact on crude oil viscosity and even the economic value of the fluids in the reservoir. Thus, it is highly desirable to understand the primary controls on crude oil composition and asphaltene distributions in reservoirs. Here, a complex oilfield in the North Sea containing six separate reservoirs is addressed. The crude oil is believed to have spilled out of deeper reservoirs into shallower reservoirs during the overall reservoir charging process. Asphaltene content is measured in-situ through downhole fluid analysis and is generally consistent with a spill-fill sequence in reservoir charging. Detailed compositional analysis of crude oil samples by comprehensive two-dimensional gas chromatography (GC×GC) is used to determine the extent and variation among the reservoirs of water washing, biodegradation and thermal maturity. Increased biodegradation and water washing in the shallower reservoirs is consistent with a spill-fill sequence. The water washing is evidently assisted by biodegradation. Moreover, analyses of four thermal maturity biomarkers show that shallower reservoirs contain less mature oil, again consistent with a spill-fill sequence. The combination of DFA for bulk compositional analysis and GC×GC for detailed compositional analysis with geochemical interpretation is an effective tool for unraveling complex oilfield scenarios

Nitrogen chemical structure in DNA and related molecules by X-ray absorption spectroscopy

The electronic environment of nitrogen in nucleic acid bases, nucleotides, polynucleotides and DNA has been studied, for the first time using X-Ray Absorption Near-Edge Spectroscopy (XANES). Generally, the spectra of these complex molecules consist of low energy bands corresponding to ls ~rr* transitions and high energy bands corresponding to ls ~tr* transition, as illustrated using several nitrogen model compounds. The ls--,~-* transitions show particular sensitivity to the chemical environment of the nitrogen. Oxygen substitution on ring carbon atoms generally results in a significant blue shift of the lowest Is ~ ~* bands while halogen substitution results in a small blue shift. These observations illustrate the significance of the disturbance of the aromatic ring system produced by exocyclic carbonyl groups. Direct substitution on the nitrogen frequently results in significant spectral perturbations. Differences between the spectra of the polynucleotides and the sums of spectra of the individual nucleotides point to the effects of hydrogen-bonding in complementary double-helix structures. The XANES spectrum of a DNA sample with a known ratio of the polynucleotides is equivalent to the weighted sum of the spectra of individual polynucleotides, indicating that the difference in base stacking interactions produces negligible spectral effects. The variability of nitrogen K-edge spectra in these samples and in protein may be useful for chemically specific imaging using X-ray microscopes

Temporal, Situational and Interactional Features of Women’s Violent Conflicts

This article examines contextual and situational influences on the processural development of women\u27s violent conflicts. Through close analysis of 3 women\u27s accounts of their disputes and associated violent behaviours, we provide a rich description of how such events evolved over time and how the interviewees managed this process. Drawing upon both criminological and feminist theories, our analysis highlights existing gaps in the literature, providing an exploratory discussion of the interaction of gender with situational elements and the production of assaultive events

Introductory programming: a systematic literature review

As computing becomes a mainstream discipline embedded in the school curriculum and acts as an enabler for an increasing range of academic disciplines in higher education, the literature on introductory programming is growing. Although there have been several reviews that focus on specific aspects of introductory programming, there has been no broad overview of the literature exploring recent trends across the breadth of introductory programming. This paper is the report of an ITiCSE working group that conducted a systematic review in order to gain an overview of the introductory programming literature. Partitioning the literature into papers addressing the student, teaching, the curriculum, and assessment, we explore trends, highlight advances in knowledge over the past 15 years, and indicate possible directions for future research

HIV-Specific Probabilistic Models of Protein Evolution

Comparative sequence analyses, including such fundamental bioinformatics techniques as similarity searching, sequence alignment and phylogenetic inference, have become a mainstay for researchers studying type 1 Human Immunodeficiency Virus (HIV-1) genome structure and evolution. Implicit in comparative analyses is an underlying model of evolution, and the chosen model can significantly affect the results. In general, evolutionary models describe the probabilities of replacing one amino acid character with another over a period of time. Most widely used evolutionary models for protein sequences have been derived from curated alignments of hundreds of proteins, usually based on mammalian genomes. It is unclear to what extent these empirical models are generalizable to a very different organism, such as HIV-1–the most extensively sequenced organism in existence. We developed a maximum likelihood model fitting procedure to a collection of HIV-1 alignments sampled from different viral genes, and inferred two empirical substitution models, suitable for describing between-and within-host evolution. Our procedure pools the information from multiple sequence alignments, and provided software implementation can be run efficiently in parallel on a computer cluster. We describe how the inferred substitution models can be used to generate scoring matrices suitable for alignment and similarity searches. Our models had a consistently superior fit relative to the best existing models and to parameter-rich data-driven models when benchmarked on independent HIV-1 alignments, demonstrating evolutionary biases in amino-acid substitution that are unique to HIV, and that are not captured by the existing models. The scoring matrices derived from the models showed a marked difference from common amino-acid scoring matrices. The use of an appropriate evolutionary model recovered a known viral transmission history, whereas a poorly chosen model introduced phylogenetic error. We argue that our model derivation procedure is immediately applicable to other organisms with extensive sequence data available, such as Hepatitis C and Influenza A viruses

Diagnosis and management in Rubinstein-Taybi syndrome:first international consensus statement

Rubinstein-Taybi syndrome (RTS) is an archetypical genetic syndrome that is characterised by intellectual disability, well-defined facial features, distal limb anomalies and atypical growth, among numerous other signs and symptoms. It is caused by variants in either of two genes (CREBBP, EP300) which encode for the proteins CBP and p300, which both have a function in transcription regulation and histone acetylation. As a group of international experts and national support groups dedicated to the syndrome, we realised that marked heterogeneity currently exists in clinical and molecular diagnostic approaches and care practices in various parts of the world. Here, we outline a series of recommendations that document the consensus of a group of international experts on clinical diagnostic criteria for types of RTS (RTS1: CREBBP; RTS2: EP300), molecular investigations, long-term management of various particular physical and behavioural issues and care planning. The recommendations as presented here will need to be evaluated for improvements to allow for continued optimisation of diagnostics and care.</p

Diagnosis and management in Rubinstein-Taybi syndrome:first international consensus statement

Rubinstein-Taybi syndrome (RTS) is an archetypical genetic syndrome that is characterised by intellectual disability, well-defined facial features, distal limb anomalies and atypical growth, among numerous other signs and symptoms. It is caused by variants in either of two genes (CREBBP, EP300) which encode for the proteins CBP and p300, which both have a function in transcription regulation and histone acetylation. As a group of international experts and national support groups dedicated to the syndrome, we realised that marked heterogeneity currently exists in clinical and molecular diagnostic approaches and care practices in various parts of the world. Here, we outline a series of recommendations that document the consensus of a group of international experts on clinical diagnostic criteria for types of RTS (RTS1: CREBBP; RTS2: EP300), molecular investigations, long-term management of various particular physical and behavioural issues and care planning. The recommendations as presented here will need to be evaluated for improvements to allow for continued optimisation of diagnostics and care.</p

Membrane tension controls adhesion positioning at the leading edge of cells

Cell migration is dependent on adhesion dynamics and actin cytoskeleton remodeling at the leading edge. These events may be physically constrained by the plasma membrane. Here, we show that the mechanical signal produced by an increase in plasma membrane tension triggers the positioning of new rows of adhesions at the leading edge. During protrusion, as membrane tension increases, velocity slows, and the lamellipodium buckles upward in a myosin II-independent manner. The buckling occurs between the front of the lamellipodium, where nascent adhesions are positioned in rows, and the base of the lamellipodium, where a vinculin-dependent clutch couples actin to previously positioned adhesions. As membrane tension decreases, protrusion resumes and buckling disappears, until the next cycle. We propose that the mechanical signal of membrane tension exerts upstream control in mechanotransduction by periodically compressing and relaxing the lamellipodium, leading to the positioning of adhesions at the leading edge of cells