Balance of dark and luminous mass in rotating galaxies

A fine balance between dark and baryonic mass is observed in spiral galaxies. As the contribution of the baryons to the total rotation velocity increases, the contribution of the dark matter decreases by a compensating amount. This poses a fine-tuning problem for galaxy formation models, and may point to new physics for dark matter particles or even a modification of gravity.     

Method for reducing the ambiguity of comprehensive two-dimensional chromatography retention times

Comprehensive two-dimensional chromatography generates a two-dimensional chromatogram from a one-dimensional signal array. This process can only be done unambiguously when the range of secondary retention times is less than the modulation period. However, complex samples often produce wider ranges of secondary retention times. Peaks with retention times that exceed the modulation period are said to be "wrapped-around". A simple algorithm has been developed that determines absolute retention times when wrap-around occurs. A sample is first analyzed under standard modulation conditions and then re-analyzed with a modulation period that is increased by an integer fraction of the original modulation period. Retention shifts along the secondary axis are used to determine absolute retention times. A theoretical analysis has been performed to optimize the implementation conditions and characterize the technique limitations. The efficacy of this algorithm has been tested through a series of isothermal GC x GC separations. This method has been found to be particularly useful during the initial stages of method development.     

The performance of matched-field track-before-detect methods using shallow-water Pacific data

Matched-field track-before-detect processing, which extends the concept of matched-field processing to include modeling of the source dynamics, has recently emerged as a promising approach for maintaining the track of a moving source. In this paper, optimal Bayesian and minimum variance beamforming track-before-detect algorithms which incorporate a priori knowledge of the source dynamics in addition to the underlying uncertainties in the ocean environment are presented. A Markov model is utilized for the source motion as a means of capturing the stochastic nature of the source dynamics without assuming uniform motion. In addition, the relationship between optimal Bayesian track-before-detect processing and minimum variance track-before-detect beamforming is examined, revealing how an optimal tracking philosophy may be used to guide the modification of existing beamforming techniques to incorporate track-before-detect capabilities. Further, the benefits of implementing an optimal approach over conventional methods are illustrated through application of these methods to shallow-water Pacific data collected as part of the SWellEX-1 experiment. The results show that incorporating Markovian dynamics for the source motion provides marked improvement in the ability to maintain target track without the use of a uniform velocity hypothesis.     

The effects of nonstoichiometry and electron concentration on the properties of LixHfTe2−y

In order to assess the relative contributions of excess electrons from lithium interstitials and tellurium vacancies to the electronic structure of HfTe₂, samples of Li_xHfTe_2?y were prepared by high-temperature synthesis. Powder X-ray diffraction analysis shows the hexagonal a parameter to be a weak function of surplus electron count (x + 2y), but the c parameter to be a strong function of Li content. Magnetic measurements indicate that the lithium interstitials donate more electrons to the conduction band than donated by the tellurium vacancies. Several of the samples with high surplus electron count show unusual magnetic behavior at low temperatures and low fields.     

Untargeted Metabolomics Strategies—Challenges and Emerging Directions

Metabolites are building blocks of cellular function. These species are involved in enzyme-catalyzed chemical reactions and are essential for cellular function. Upstream biological disruptions result in a series of metabolomic changes and, as such, the metabolome holds a wealth of information that is thought to be most predictive of phenotype. Uncovering this knowledge is a work in progress. The field of metabolomics is still maturing; the community has leveraged proteomics experience when applicable and developed a range of sample preparation and instrument methodology along with myriad data processing and analysis approaches. Research focuses have now shifted toward a fundamental understanding of the biology responsible for metabolomic changes. There are several types of metabolomics experiments including both targeted and untargeted analyses. While untargeted, hypothesis generating workflows exhibit many valuable attributes, challenges inherent to the approach remain. This Critical Insight comments on these challenges, focusing on the identification process of LC-MS-based untargeted metabolomics studies—specifically in mammalian systems. Biological interpretation of metabolomics data hinges on the ability to accurately identify metabolites. The range of confidence associated with identifications that is often overlooked is reviewed, and opportunities for advancing the metabolomics field are described.

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Toward fully synthetic glycoproteins by ultimately convergent routes: a solution to a long-standing problem

A method is disclosed for the convergent synthesis of multiply glycosylated peptides. The approach centers on a convergent technique for generating masked, complex glycopeptide-containing C-terminal acyl donors. Activation of the latent donor in situ and use directly in segment coupling with a second peptide bearing a complex carbohydrate produces a completely unprotected, bifunctional glycopeptide. The system demonstrates a minimum level of hydrolysis and epimerization at the C-terminal amino acid residue of the acyl donor during fully convergent segment coupling and is therefore a powerful tool for the synthesis of glycoproteins.     

Discovery of a potent,non-peptide bradykinin B1 receptor antagonist

Bradykinin (BK) plays an important role in the pathophysiological processes accompanying pain and inflammation. Selective bradykinin B1 receptor antagonists have been shown to be anti-nociceptive in animal models and could be novel therapeutic agents for the treatment of pain and inflammation. We have explored chemical modifications in a series of dihydroquinoxalinone sulfonamides to evaluate the effects of various structural changes on biological activity. The optimization of a screening lead compound, facilitated by a homology model of the BK B1 receptor, culminated in the discovery of a potent human BK B1 receptor antagonist. Results from site-directed mutagenesis studies and experiments in an animal pain model are presented.     

The preparation, characterization and X-ray structural analysis of tetrakis[1-methyl-3-(2-propyl)-2(3H)-imidazolethione]zinc(II) tetrafluoroborate and tetrakis[1-methyl-3-(1-butyl)-2(3H)- imidazolethione]zinc(II) tetrafluoroborate

Two compounds, [Zn(mipit)₄][BF₄]₂ (1) and [Zn(mnbit)₄][BF₄]₂ (2) have been synthesized and characterized via standard solid and solution state methods including single crystal X-ray crystallography (mipit: 1-methyl-3-(2-propyl)-2(3H)-imidazolethione and mnbit: 1-methyl-3-(1-butyl)-2(3H)-imidazolethione). Compound 1 crystallizes in monoclinic space group P2₁/n with a = 11.804(2) ?, b = 16.710(3) ?, c = 25.763(5) ?, γ = 90.14(3)° and Z = 4, whereas compound 2 crystallizes in tetragonal space group $${\rm I}\bar{4}$$ with a = b = 11.6517(16) ?, c= 16.820(3) ?, and Z = 2. Both complexes are high melting, colorless water soluble 2:1 electrolyte solids that state have flattened tetrahedral ZnS₄ coordination geometry. The isopropyl analog is slightly more distorted than the n-butyl analog, and the degree of distortion is not directly related to the steric bulk of the ligand.