Publications

High molecular mass polystannanes via dehydropolymerization of di(n-butyl)stannane

The dehydropolymerization of Bun2SnH2, catalysed by [Zr(C5H5)(C5Me5){Si(SiMe3)3}Me], produces cyclic (SnBun2)n oligomers and long H(SnBun2)nH polystannane chains (MwMn= 17 500/7800), which exhibit a long-wavelength electronic absorption (λmax= 382 nm) and emit green light (λmax= 505 nm; 337.1 nm excitation).

Consuming fructose-sweetened, not glucose-sweetened, beverages increases visceral adiposity and lipids and decreases insulin sensitivity in overweight/obese humans

Studies in animals have documented that, compared with glucose, dietary fructose induces dyslipidemia and insulin resistance. To assess the relative effects of these dietary sugars during sustained consumption in humans, overweight and obese subjects consumed glucose- or fructose-sweetened beverages providing 25% of energy requirements for 10 weeks. Although both groups exhibited similar weight gain during the intervention, visceral adipose volume was significantly increased only in subjects consuming fructose. Fasting plasma triglyceride concentrations increased by approximately 10% during 10 weeks of glucose consumption but not after fructose consumption. In contrast, hepatic de novo lipogenesis (DNL) and the 23-hour postprandial triglyceride AUC were increased specifically during fructose consumption. Similarly, markers of altered lipid metabolism and lipoprotein remodeling, including fasting apoB, LDL, small dense LDL, oxidized LDL, and postprandial concentrations of remnant-like particle-triglyceride and -cholesterol significantly increased during fructose but not glucose consumption. In addition, fasting plasma glucose and insulin levels increased and insulin sensitivity decreased in subjects consuming fructose but not in those consuming glucose. These data suggest that dietary fructose specifically increases DNL, promotes dyslipidemia, decreases insulin sensitivity, and increases visceral adiposity in overweight/obese adults.

CCDC 719120: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Changes in Photosynthetic Capacity and Photosynthetic Protein Pattern during Tomato Fruit Ripening

Levels of polypeptides participating in the photosynthetic light and dark reactions have been measured during fruit ripening in tomato. Photosynthetic proteins were identified by Western blot analysis with heterologous antibodies. The concentrations of proteins of photosystem (PS) I (14 kilodaltons), of PSII (47-kilodalton reaction center protein, 32-kilodalton ;Q(B) binding' protein and light harvesting complex proteins), of the photosynthetic electron transport chain (ferredoxin-NADP-oxidoreductase and plastocyanin), and of the stroma (ribulose-1,5-bisphosphate carboxylase) decrease during the ripening process. The 32-kilodalton protein and plastocyanin were detectable in pericarp protein preparations of ripe tomato fruits. Absorbance difference spectrophotometry provided information on the relative concentrations of PSII and PSI reaction centers in leaf and green fruit tissue of tomato. These results indicate that green fruit pericarp of tomato is photosynthetically active. Photosynthetic activity decreases during chloroplast/chromoplast differentiation. This is consistent with changes that occur at the transcript level of photosynthesis-specific proteins during the differentiation process.

A test of the bidirectional association between sleep and mood in bipolar disorder and insomnia.

The present study investigates sleep, mood, and the proposed bidirectional relationship between the two in psychiatric disorders. Participants with interepisode bipolar disorder (n = 49), insomnia (n = 34), and no psychiatric history (n = 52) completed seven consecutive days of sleep diaries and mood measures. The interepisode bipolar and insomnia participants exhibited greater sleep disturbance than the healthy control individuals. Negative mood was equally heightened in both interepisode bipolar disorder and insomnia, and there were no differences between the three groups in positive mood. Total wake time was associated with next morning negative mood in bipolar disorder, whereas evening negative mood was associated with subsequent total wake time in both bipolar disorder and insomnia. Additionally, positive mood was associated with subsequent total wake time for the insomnia group. Results support the theory that disruptions in nighttime sleep and daytime mood may be mutually maintaining and suggest the potential importance of transdiagnostic or universal processes.

Mastocitosis sistémicas

ACTH therapy in some nonhypsarrhythmic forms of epilepsy.

CCDC 1003084: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Nickel N-heterocyclic carbene–pyridine complexes that exhibit selectivity for electrocatalytic reduction of carbon dioxide over water

We report a homologous series of nickel(II) complexes supported by N-heterocyclic carbene-pyridine ((R)bimpy, R = Me, Et, Pr) ligands that exhibit high selectivity for reducing carbon dioxide over water under electrocatalytic conditions.

Isotherms of individual pores by gas adsorption crystallography

An Analysis of Professor J.F. Bell's Research on the Finite Twist and Extension of Thin-walled Polycrystalline Cylindrical Tubes

Ultra-Fast Evaluation of Protein Energies Directly from Sequence

The structure, function, stability, and many other properties of a protein in a fixed environment are fully specified by its sequence, but in a manner that is difficult to discern. We present a general approach for rapidly mapping sequences directly to their energies on a pre-specified rigid backbone, an important sub-problem in computational protein design and in some methods for protein structure prediction. The cluster expansion (CE) method that we employ can, in principle, be extended to model any computable or measurable protein property directly as a function of sequence. Here we show how CE can be applied to the problem of computational protein design, and use it to derive excellent approximations of physical potentials. The approach provides several attractive advantages. First, following a one-time derivation of a CE expansion, the amount of time necessary to evaluate the energy of a sequence adopting a specified backbone conformation is reduced by a factor of 10(7) compared to standard full-atom methods for the same task. Second, the agreement between two full-atom methods that we tested and their CE sequence-based expressions is very high (root mean square deviation 1.1-4.7 kcal/mol, R2 = 0.7-1.0). Third, the functional form of the CE energy expression is such that individual terms of the expansion have clear physical interpretations. We derived expressions for the energies of three classic protein design targets-a coiled coil, a zinc finger, and a WW domain-as functions of sequence, and examined the most significant terms. Single-residue and residue-pair interactions are sufficient to accurately capture the energetics of the dimeric coiled coil, whereas higher-order contributions are important for the two more globular folds. For the task of designing novel zinc-finger sequences, a CE-derived energy function provides significantly better solutions than a standard design protocol, in comparable computation time. Given these advantages, CE is likely to find many uses in computational structural modeling.

Some Footnotes to the Optimization-based Calibration of the 40 Ar/ 39 Ar System

Abstract: A recent calibration of the 40Ar/39Ar geochronometer is based on an optimiza-tion analysis of 40K activity data, isotopic data for the Fish Canyon sanidine (FCs) standard, and pairs of 40Ar/39Ar + 238U–206Pb data from selected samples meeting well-documented quality criteria. Inclusion of 238U–206Pb data in the calibration incorporates the precisely known 238U decay constant. Thus, this calibration is inherently consistent with the U–Pb chronometer. Initial presentation of the calibration included an inappropriate datum and should be eschewed in preference to a revision. Compared with previous calibrations, including those focusing mainly on the age of a standard (e.g. astronomical calibrations), the optimization calibration provides superior accuracy in the sense of propagated age uncertainty, particularly for ages much older than the FCs. Recent literature reveals that the optimization-based calibration has been misused and misrepresented in some cases; discussion of these cases clarifies the correct usage of the approach. Apparent conflict between 40Ar/39Ar and 238U–206Pb ages for a Quaternary tuff do not appear to be a result of error in one of the three parameters determined by the optim-ization approach for the 40Ar/39Ar system. The optimization approach easily accommodates new constraints, but rigorous quality control is needed to maintain accuracy.

GRB 080727B: KAIT photometry and an early lightcurve break.

Computational understanding of Li-ion batteries

Abstract Over the last two decades, computational methods have made tremendous advances, and today many key properties of lithium-ion batteries can be accurately predicted by first principles calculations. For this reason, computations have become a cornerstone of battery-related research by providing insight into fundamental processes that are not otherwise accessible, such as ionic diffusion mechanisms and electronic structure effects, as well as a quantitative comparison with experimental results. The aim of this review is to provide an overview of state-of-the-art ab initio approaches for the modelling of battery materials. We consider techniques for the computation of equilibrium cell voltages, 0-Kelvin and finite-temperature voltage profiles, ionic mobility and thermal and electrolyte stability. The strengths and weaknesses of different electronic structure methods, such as DFT+U and hybrid functionals, are discussed in the context of voltage and phase diagram predictions, and we review the merits of lattice models for the evaluation of finite-temperature thermodynamics and kinetics. With such a complete set of methods at hand, first principles calculations of ordered, crystalline solids, i.e., of most electrode materials and solid electrolytes, have become reliable and quantitative. However, the description of molecular materials and disordered or amorphous phases remains an important challenge. We highlight recent exciting progress in this area, especially regarding the modelling of organic electrolytes and solid–electrolyte interfaces.

Use of Nonionic Surfactants for Improvement of Terpene Production in Saccharomyces cerevisiae

ABSTRACT To facilitate enzyme and pathway engineering, a selection was developed for improved sesquiterpene titers in Saccharomyces cerevisiae . α-Bisabolene, a candidate advanced biofuel, was found to protect yeast against the disruptive action of nonionic surfactants such as Tween 20 (T20). An experiment employing competition between two strains of yeast, one of which makes twice as much bisabolene as the other, demonstrated that growth in the presence of T20 provided sufficient selective pressure to enrich the high-titer strain to form 97% of the population. Following this, various methods were used to mutagenize the bisabolene synthase (BIS) coding sequence, coupled with selection by subculturing in the presence of T20. Mutagenesis targeting the BIS active site did not yield an improvement in bisabolene titers, although mutants were found which made a mixture of α-bisabolene and β-farnesene, another candidate biofuel. Based on evidence that the 3′ end of the BIS mRNA may be unstable in yeast, we randomly recoded the last 20 amino acids of the enzyme and, following selection in T20, found a variant which increased specific production of bisabolene by more than 30%. Since T20 could enrich a mixed population, efficiently removing strains that produced little or no bisabolene, we investigated whether it could also be applied to sustain high product titers in a monoculture for an extended period. Cultures grown in the presence of T20 for 14 days produced bisabolene at titers up to 4-fold higher than cultures grown with an overlay of dodecane, used to sequester the terpene product, and 20-fold higher than cultures grown without dodecane.

Evaluation of Fractal Models To Describe Reservoir Heterogeneity and Performance

Summary Our work uses fractals to characterize the spatial correlation structures of porosity and permeability of vertical and horizontal logs in a braided-fluvial sandstone reservoir. The data comprise cores and logs of adjacent vertical wells and logs of horizontal wells. Small-scale realizations of interwell heterogeneity were generated with successive random additions (SRA) technique for new observed fractal models. A deterministic description is also developed. Effects of fractal and deterministic reservoir heterogeneity on reservoir performance were studied for waterflood and water-alternating-gas (WAG) injection processes. The effects of scale up on spatial correlation of porosity was investigated. The fractal model of fractional Brownian motion (FBM) in the horizontal direction, having same intermittency exponent as for fractional Gaussian noise (FGN) in the vertical direction, is not supported by log observations in horizontal wells. Fractal character of core and log data of vertical wells is similar. The incremental WAG recovery response compared to waterflooding response is more sensitive to reservoir heterogeneity. Scale-up experiments indicate that spatial correlation structure of reservoir properties may be different at different scales. Results of this paper will be useful for evaluation of infill drilling, and design, selection, and optimization of an EOR process. The proposed techniques also provide a framework to quantify uncertainty in reservoir performance.

Terpene Hydrocarbons Production in Cyanobacteria