A possible role for MRI in polyarteritis nodosa: The “creeping fat” sign

We describe a case of polyarteritis nodosa with diffuse abnormalities in subcutaneous fat by magnetic resonance imaging. These abnormalities returned to normal following treatment. Magnetic resonance imaging may have a role in the identification and diagnosis of systemic vasculitis.     

Design and testing of a microtitration assembly for use with an LKB Batch Microcalorimeter

A twin, automatic microtitration assembly suitable for use with an LKB Batch Microcalorimeter is described. The apparatus, which can accurately and reproducibly deliver volumes as low as 1 μl, permits up to 20 titration additions to be made. It has been tested by the determination of the heat of ionisation of water at 303.15±0.01 K. The value determined compares favourably with the “best” value reported in the literature.     

RuII complexes incorporating tetrathiamacrocycles: synthesis and conformational analysis

The synthesis of a series of RuII complexes incorporating thiacrown ligands ([12]ane-S4, [14]ane-S4, [16]ane-S4), as well as 2,2'-bipyridine (bpy) or pyridine, is reported. Structural studies on these complexes have been carried out using a variety of techniques. Detailed 1H NMR spectroscopic studies on the previously reported [Ru([12]ane-S4)(bpy)]2+ (1) reveal that-contrary to earlier reports-the observed fluxional 1H NMR behavior is not due to chemical exchange involving cleavage of the bpy Ru--N bond but is, in fact, due to lone-pair inversion of coordinated macrocyclic sulfur donor atoms. This phenomenon is also observed for the [14]ane-S4 and [16]ane-S4 analogues of 1. For the first time, using a combination of X-ray crystallography, more detailed 1H NMR experiments, and computational methods, an in-depth study on the energetics and dynamics of invertomer formation and conversion for macrocyclic coordination complexes has been carried out. These studies reveal that the steric constraints of assembling each sulfur macrocycle and bpy ligand around the octahedral Ru(II) center lead to close intramolecular contacts. These contacts are largely dependent on the orientation of the electron lone pairs of equatorial sulfur donor atoms and correlate with the comparative stability of the different invertomeric forms. Thus, the conformational preferences of the three macrocyles in [Ru([n]ane-S4)(bpy)]2+ complexes are determined by steric rather than electronic effects.     

Cross sections and oscillator strengths for electron-impact excitation of the A 1B1 electronic state of water

The authors report absolute differential and integral cross section measurements for electron-impact excitation of the A (1)B(1) electronic state of water. This is an important channel for the production of the OH (X (2)Pi) radical, as well as for understanding the origin of the atmospheric Meinel [Astrophys. J. 111, 555 (1950)] bands. The incident energy range of our measurements is 20-200 eV, while the angular range of the differential cross section data is 3.5 degrees -90 degrees . This is the first time such data are reported in the literature and, where possible, comparison to existing theoretical work, and new scaled Born cross sections calculated as a part of the current study, is made. The scaled Born cross sections are in good agreement with the integral cross sections deduced from the experimental differential cross sections. In addition they report (experimental) generalized oscillator strength data at the incident energies of 100 and 200 eV. These data are used to derive a value for the optical oscillator strength which is found to be in excellent agreement with that from an earlier dipole (e,e) experiment and an earlier photoabsorption experiment.     

Prediction of refrigerant void fraction in horizontal tubes using probabilistic flow regime maps

A state of the art review of two-phase void fraction models in smooth horizontal tubes is provided and a probabilistic two-phase flow regime map void fraction model is developed for refrigerants under condensation, adiabatic, and evaporation conditions in smooth, horizontal tubes. Time fraction information from a generalized probabilistic two-phase flow map is used to provide a physically based weighting of void fraction models for different flow regimes. The present model and void fraction models in the literature are compared to data from multiple sources including R11, R12, R134a, R22, R410A refrigerants, 4.26–9.58 mm diameter tubes, mass fluxes from 70 to 900 kg/m² s, and a full quality range. The present model has a mean absolute deviation of 3.5% when compared to the collected database.     

BertiniLab: A MATLAB interface for solving systems of polynomial equations

A MATLAB interface to the numerical homotopy continuation package Bertini is described. Bertini solves systems of polynomial equations. BertiniLab can be used to create input files for Bertini, run Bertini and process the solutions. All features of Bertini 1.5 are supported. The user can define the system of equations using a MATLAB numerical function, and vector and matrix operations are allowed. An object-oriented design allows the user to separate the statement of the problem from the details of the solution; the user can create subclasses to provide shortcuts or to tailor BertiniLab to a specific kind of problem. A complete example of an application to ferromagnetism is presented.     

Effects on peptide binding affinity for TNFα by PEGylation and conjugation to hyaluronic acid

Conjugation of cytokine-neutralizing monoclonal antibodies (mAb) to hyaluronic acid (HA) having M_w of 1.6 MDa was previously shown to be an effective strategy for localized delivery to sites of inflammation. Despite the disparity in size of the mAb and HA, the mAb–HA conjugate was found bind tumor necrosis factor-α (TNFα) as strongly as the non-conjugated antibody, suggesting conjugation to this charged polysaccharide can provide an alternative to poly(ethylene glycol) (PEG) conjugation, which has been shown to reduce binding interactions for many proteins. To explore conjugation chemistries more systematically, we report a study on a model peptide inhibitor of tumor necrosis factor-α to investigate the effects of site-specific conjugation to HA and PEG. We compared the binding affinities of a variety of WP9QY peptide–polymer conjugates for TNFα in order to examine the effects of PEG molecular weight as well as the effects of PEG versus functionalized hyaluronic acid (HA) conjugation. The results indicate that the binding affinity of the PEG conjugates decreases in comparing PEG with mass 2 k, 10 k, and 30 k, which was attributed to PEG shrouding of the peptide, while conjugation to a 66 kDa HA chain preserved peptide binding affinity. We attribute this difference to the increased solubility of HA compared to PEG, potentially due to the carboxylic acid functional groups. In addition, the results demonstrate that conjugation to HA via a short PEG linker significantly enhances the association rate k_on, which may reflect an increased peptide accessibility. By balancing both the advantages associated with the PEG conjugates and with the HA conjugates, the HA–PEG2k–WP9QY conjugate was able to improve the binding affinity of the peptide for TNFα by a factor of two. Optimization of polymer chemistry could be used to improve delivery of protein therapeutics for localized and systemic administration.     

Cryogenic OrbiSIMS Localizes Semi‐Volatile Molecules in Biological Tissues

OrbiSIMS is a recently developed instrument for label‐free imaging of chemicals with micron spatial resolution and high mass resolution. We report a cryogenic workflow for OrbiSIMS (Cryo‐OrbiSIMS) that improves chemical detection of lipids and other biomolecules in tissues. Cryo‐OrbiSIMS boosts ionization yield and decreases ion‐beam induced fragmentation, greatly improving the detection of biomolecules such as triacylglycerides. It also increases chemical coverage to include molecules with intermediate or high vapor pressures, such as free fatty acids and semi‐volatile organic compounds (SVOCs). We find that Cryo‐OrbiSIMS reveals the hitherto unknown localization patterns of SVOCs with high spatial and chemical resolution in diverse plant, animal, and human tissues. We also show that Cryo‐OrbiSIMS can be combined with genetic analysis to identify enzymes regulating SVOC metabolism. Cryo‐OrbiSIMS is applicable to high resolution imaging of a wide variety of non‐volatile and semi‐volatile molecules across many areas of biomedicine.