Blood Stored In EDTA Tubes Provides Accurate Peanut Basophil Activation Test Results For 48 hours.

BACKGROUND: The peanut basophil activation test (BAT) has demonstrated excellent diagnostic accuracy with heparinized blood, but its clinical utility is limited by the short stability of samples stored in this anticoagulant. OBJECTIVE: Using EDTA anticoagulated blood, these investigations determined if Peanut BAT sample stability can be extended to 2 days, the minimum stability requirement for diagnostic tests currently offered through American reference laboratories. METHODS: Peanut non-allergic control (NAC), peanut IgE sensitized (PS), and peanut allergic (PA) children aged 6 months through 17 years were recruited from members of Kaiser Permanente Southern California. EDTA anti-coagulated blood samples were collected from participants, shipped to a centralized laboratory, and stored at 4oC for peanut BAT testing 1 and 2 days later. RESULTS: Peanut BAT results for 23 unblinded participants were used to establish sample rejection and interpretation criteria that were subsequently validated in a prospective double-blind study involving 112 additional children (39-NAC, 36-PS, 37-PA). Of 105 blinded blood samples tested on each study day, 88 (84%) day-1 and 90 (86%) day-2 peanut BAT results were considered interpretable, with diagnostic accuracies of 95.5% and 94.4%, respectively. Moreover, all interpretable PA results were considered positive (100% sensitivity). CONCLUSION: Using EDTA anti-coagulated blood samples collected remotely, 1 and 2 days before testing, study results highlight the favorable diagnostic performance characteristics of the peanut BAT and provide further evidence that the test could be readily operationalized for clinical use by interested commercial reference laboratories.

Synthesis, Characterization, and Single-Crystal X-ray Structures of Refractory Metal Compounds as Precursors for the Single-Source Chemical Vapor Deposition of Metal Nitrides.

The chemical vapor deposition of refractory metal nitrides requires volatile precursors and has previously been achieved by using metal complexes containing a variety of imide ligands. Recently, the 1,4-di-tert-butyl-1,3-diazabutadiene (DAD) adduct of bis(tert-butylimide)dichloridemolybdenum(VI) was shown to be an excellent precursor for the single-source CVD of Mo2N thin films. Leveraging the success of this work, we prepared chromium and tungsten compounds with the same framework. Additionally, the framework has been modified slightly to allow the isolation of mono(tert-butylimide)trichloride complexes of vanadium, niobium, tantalum, and molybdenum(V) to extend the search for new vapor-phase precursors. These compounds were all fully characterized using the standard methods of multinuclear magnetic resonance spectroscopy, combustion analysis, and single-crystal X-ray diffraction. Their thermal properties were determined by using thermogravimetric analysis and differential scanning colorimetry to assess their utility as vapor-phase precursors. Finally, preliminary deposition studies were carried out to investigate their potential as single-source CVD precursors.

PI and PIII Ions Supported by BZIMPY Ligands.

We report a class of compounds in which both PIII -X and PI forms featuring the same ligand are stable and readily cycled with each other. A series of PIII -X (X=Cl, Br, I) dicationic triflate salts supported by benzyl- and allyl-substituted 2,6-bis(benzimidazole-2-yl)pyridine (BZIMPY) ligands is synthesized. Surprisingly, treatment of these with R3 PO (R=Et, Oct) results in reduction to BZIMPY-ligated PI monocationic triflate salts while treatment with Ph3 P reduces but also substitutes the compound to produce Ph3 P-BZIMPY-ligated PI dicationic triflate salts. The mechanisms of these surprising reductions are probed experimentally and rationalized computationally. The PIII -X dications are shown to be strong Lewis acids both experimentally and computationally and to readily behave as X+ , PX, and P+ transfer agents in reactions with phosphines, NHCs, and diazabutadienes. The PI mono- and dications are shown to be very effective P+ transfer agents when treated similarly. Oxidation from a monocationic PI salt back to the dicationic PIII -X (X=Cl, Br) salt was achieved by treatment with N-chlorosuccinimide (NCS) or N-bromosuccinimide (NBS). Full characterization is reported using multinuclear nuclear magnetic resonance spectroscopy, elemental analysis, and single-crystal X-ray diffractometry where suitable crystals were isolated.

An Improved Synthesis of PN-adamantanoid Cages P4 (NR)6 and a Mechanistic Study of their Fourfold Oxidation.

Phosphorus-nitrogen (PN) adamantanoid cages are valuable precursors for materials chemistry, but their syntheses are based on harsh methods that sometimes require access to restricted reagents. We report a new and scalable synthesis of PN adamantanoid compounds by chlorosilane elimination between bis-silylated amines and phosphorus trichloride. We further study the mechanism of the recently-reported four-fold oxidation of such cages with Me3 SiN3 to yield tetravalent tetrahedral connectors for materials chemistry. Reaction monitoring and kinetic modelling revealed the key rate-limiting step, but attempts to accelerate this using Lewis acid additives were unsuccessful. Nevertheless, a new four-fold oxidized PN-adamantanoid cage has been prepared and structurally characterized.

Disturbance of intermolecular forces: eutectics as a new tool for the preparation of vapor-phase deposition precursors.

The volatile bis(tert-butylimido)dichloromolybdenum(VI) compounds, (tBuN)2MoCl2·dad (dad = 1,4-di-tert-butyl-1,3-diazabutadiene) (1) and [(tBuN)2MoCl(µ-Cl)·(tBuNH2)]2 (2), form a eutectic, with a two to one composition (χ2 = 0.33). A decrease of 40 °C in the melting temperature has been observed between the eutectic mixture and the pure compounds. We have isolated a co-crystal of (tBuN)2MoCl2·dme (dme = 1,2-dimethoxyethane) (3) and 2, also in a two to one ratio, which serves as a structural model for such mixtures. The lower melting point of carefully chosen eutectic mixtures can offer more consistent precursor delivery in deposition processes.

Origin of Decomposition in a Family of Molybdenum Precursor Compounds.

The bis(tert-butylimido)-molybdenum(VI) framework has been used successfully in the design of vapor-phase precursors for molybdenum-containing thin films, so understanding its thermal behavior is important for such applications. Here, we report the thermal decomposition mechanism for a series of volatile bis(alkylimido)-dichloromolybdenum(VI) adducts with neutral N,N'-chelating ligands, to probe the stability and decomposition pathways for these molecules. The alkyl groups explored were tert-butyl, tert-pentyl, 1-adamantyl, and a cyclic imido (from 2,5-dimethylhexane-2,5-diamine). We also report the synthesis of the new tert-octyl imido adducts, (tOctN)2MoCl2·L (L = N,N,N',N'-tetramethylethylenediamine or 2,2'-bipyridine), which have been fully characterized by spectroscopic techniques as well as single-crystal X-ray diffraction and thermal analysis. We found that the decomposition of all compounds follows the same general pathway, proceeding first by the dissociation of the chelating ligand to give the coordinatively unsaturated species (RN)2MoCl2. Subsequent dimerization results in either an imido bridged adduct, [(RN)Mo(µ-NR)Cl2]2, or a chloride bridged adduct, [(RN)2Mo(µ-Cl)Cl]2, depending on the size of the R group. The dimeric species then likely undergoes an intramolecular γ-hydrogen transfer to yield a nitrido-amido adduct, (RHN)MoNCl2, and an alkene. Ultimately, the resulting molybdenum species appears to decompose into free tert-alkylamine and Mo2N or Mo2C. The thermolysis reactions have been monitored using 1H NMR spectroscopy, and the volatile decomposition products were analyzed using gas chromatography-mass spectrometry. A key intermediate has also been detected using electron ionization high-resolution mass spectrometry. Finally, a detailed computational investigation supports the mechanism outlined above and helps explain the relative stabilities of different N,N'-chelated bis(alkylimido)-dichloromolybdenum(VI) adducts.

Thermal Stability and Decomposition Pathways in Volatile Molybdenum(VI) Bis-imides.

The vapor deposition of many molybdenum-containing films relies on the delivery of volatile compounds with the general bis(tert-butylimido)molybdenum(VI) framework, both in atomic layer deposition and chemical vapor deposition. We have prepared a series of (tBuN)2MoCl2 adducts using neutral N,N'-chelates and investigated their volatility, thermal stability, and decomposition pathways. Volatility has been determined by thermogravimetric analysis, with the 1,4-di-tert-butyl-1,3-diazabutadiene adduct (5) found to be the most volatile (1 Torr of vapor pressure at 135 °C). Thermal stability was measured primarily using differential scanning calorimetry, and the 1,10-phenanthroline adduct (4) was found to be the most stable with an onset of decomposition of 303 °C. We have also investigated molybdenum compounds with other alkyl-substituted imido groups: these compounds all follow a similar decomposition pathway, γ-H activation, with varying reaction barriers. The tert-pentyl, 1-adamantyl, and a cyclic imido (from 2,5-dimethylhexane-2,5-diamine) were systematically studied to probe the kinetics of this pathway. All of these compounds have been fully characterized, including via single-crystal X-ray diffraction, and a total of 19 new structures are reported.

Geostatistical Mapping of Salinity Conditioned on Borehole Logs, Montebello Oil Field, California.

We present a geostatistics-based stochastic salinity estimation framework for the Montebello Oil Field that capitalizes on available total dissolved solids (TDS) data from groundwater samples as well as electrical resistivity (ER) data from borehole logging. Data from TDS samples (n = 4924) was coded into an indicator framework based on falling below four selected thresholds (500, 1000, 3000, and 10,000 mg/L). Collocated TDS-ER data from the surrounding groundwater basin were then employed to produce a kernel density estimator to establish conditional probabilities for ER data (n = 8 boreholes) falling below the selected TDS thresholds within the Montebello Oil Field area. Directional variograms were estimated from these indicator coded data, and 500 TDS realizations from conditional indicator simulation were generated for the subsurface region above the Montebello Oil Field reservoir. Simulations were summarized as 3D maps of median TDS, most likely salinity class, and probability for exceeding each of the specified TDS thresholds. Results suggested TDS was below 500 mg/L in most of the study area, with a trend toward higher values (500 to 1000 mg/L) to the southwest; consistent with the average regional groundwater flow direction. Discrete localized zones of TDS greater than 1000 mg/L were observed, with one of these zones in the greater than 10,000 mg/L range; however, these areas were not prevalent. The probabilistic approach used here is adaptable and is readily modified to include additional data and types and can be employed in time-lapse salinity modeling through Bayesian updating.

Heavy Metals Make a Chain: A Catenated Bismuth Compound.

Catenation is common for the light main-group elements whereas it is rare for the heavy elements. Herein, we report the first example of a neutral molecule containing a Bi4 chain. It is prepared in a one-step reaction between bismuth trichloride and bis(diisopropylphosphino)amine in methanol suspension. The same reaction carried out in dichloromethane gives quite different products. All products have been characterized spectroscopically and using single-crystal X-ray analysis.

Eye movements in man and other animals.

Good vision requires a near stationary image if motion blur is to be avoided. All animals with good eyesight (principally the vertebrates, arthropods and cephalopod molluscs) have adopted a very similar strategy for achieving this: fixations in which gaze is kept still, with saccades to change gaze direction as fast as possible. In all these groups the stability of fixations is maintained by reflexes that oppose the effects of head or body movement (the vestibulo-ocular reflex in vertebrates), and that oppose drift of the image on the retina (optokinetic and optomotor reflexes). A small number of species of molluscs and arthropods have adopted a different strategy: allowing the retinas to scan across the surroundings to acquire information. The retinas in these animals are all linear structures a few receptors wide, and scan at right angles to their long dimension. The speed of scanning varies with retinal resolution, ensuring that scan speed does not produce deleterious blur.

The Evolution of Gaze Shifting Eye Movements.

In animals with good eyesight most eye movements consist of saccades, which rapidly shift the direction of the eye's axis, and intervals between the saccades (fixations) in which gaze is kept stationary relative to the surroundings. This stability is needed to prevent motion blur, and it is achieved by reflexes which counter-rotate the eye when the head moves. This saccade-and-fixate strategy arose early in fish evolution, when the original function of saccades was to re-centre the eye as the fish turned. In primates, and other foveate vertebrates, saccades took on the new function of directing the fovea to objects of interest in the surroundings. Among invertebrates the same saccade-and-fixate pattern is seen, especially in insects, crustaceans and cephalopod molluscs.

Coordination, reactivity, and structural properties of electron-rich ethoxy- and dimethylamino-substituted 1,3-diketiminate ligands and their complexes.

In this paper we describe the synthesis, characterization, and X-ray crystal structures of two ligands, diethyl-N,N'-bis(p-tolyl)malonimidate and 1,3-bis(dimethylamino)-N,N'-bis(p-tolyl)propanediimidate. Their corresponding rhodium(i) dicarbonyl, dimethylaluminium, and bis-ligated zinc complexes have also been prepared and characterized. The donor properties of the ligands have been studied and have been compared to those of the traditional anionic N,N'-chelating ligand nacnac.

Complementary and Alternative Medicine Use Among Allergy Practices: Results of a Nationwide Survey of Allergists.

The use of complementary and alternative practices in the field of Allergy/Immunology is growing. A recent survey of American Academy of Allergy, Asthma, and Immunology members examining patterns of complementary and alternative medicine (CAM) use and adverse effects from CAM revealed that a majority of practitioners (81% of respondents) had patients who are using CAM therapies over conventional treatments and many practitioners (60% of survey respondents) have encountered patients experiencing adverse reactions. During routine office visits, a majority of practitioners do not ask patients about CAM use, and when they do, most do not have a standard intake form to take a CAM history. There is a strong need to increase knowledge and improve measures to prevent adverse reactions to CAMs.

Crystal structure of 2,4,6-tri-methyl-benzoic anhydride.

The title compound, C20H22O3, was formed in the reaction between 2,4,6-tri-methyl-benzoic acid and N,N-diiso-propyl-ethyl-amine in the presence of 1,3-di-chloro-1,3-bis-(di-methyl-amino)-propenium hydrogen dichloride, and was recrystallized from diethyl ether solution. It is the first exclusively alkyl-substituted benzoic anhydride to have been structurally characterized. The asymmetric unit consists of a half mol-ecule, the other half of which is generated by twofold rotation symmetry; the dihedral angle between the symmetry-related aromatic rings is 54.97 (3)°. The geometric parameters of the aromatic ring are typical of those for 2,4,6-tri-methyl-phenyl substituted groups. The C=O and C-O bond lengths are 1.1934 (12) and 1.3958 (11) Å, respectively, and the angle between these three atoms (O=C-O) is 121.24 (9)°. In the crystal, mol-ecules are linked by weak C-H⋯O hydrogen bonds and C-H⋯π inter-actions. The packing features wavy chains that extend parallel to [001].

The current state of food allergy therapeutics.

The prevalence of IgE mediated food allergy is an increasing public health concern. The current standard of treatment is strict avoidance of the offending food(s). There are no FDA approved treatments for food allergy. This review will provide an overview of strategies currently under investigation for the treatment of food allergy. The main focus of research has been directed at various forms of immunotherapy, including oral, sublingual and epicutaneous delivery routes. While oral immunotherapy (OIT) has shown the greatest promise for efficacy in terms of amount of protein that can be ingested, it has also demonstrated less tolerability and a less favorable safety profile as compared to sublingual immunotherapy (SLIT) and epicutaneous immunotherapy (EPIT), which offers the least protection but has the best safety and tolerability profile. Investigation is also underway for modified antigens that may be used for immunotherapy and for adjuncts that may help facilitate immunotherapy, including biologics such as anti-IgE therapy, and also probiotics. There are also a number of preclinical concepts that are being evaluated to manipulate the antigens and/or the immune system that may one day be translatable to patients.

Arthropod eyes: The early Cambrian fossil record and divergent evolution of visual systems.

Four types of eyes serve the visual neuropils of extant arthropods: compound retinas composed of adjacent facets; a visual surface populated by spaced eyelets; a smooth transparent cuticle providing inwardly directed lens cylinders; and single-lens eyes. The first type is a characteristic of pancrustaceans, the eyes of which comprise lenses arranged as hexagonal or rectilinear arrays, each lens crowning 8-9 photoreceptor neurons. Except for Scutigeromorpha, the second type typifies Myriapoda whose relatively large eyelets surmount numerous photoreceptive rhabdoms stacked together as tiers. Scutigeromorph eyes are facetted, each lens crowning some dozen photoreceptor neurons of a modified apposition-type eye. Extant chelicerate eyes are single-lensed except in xiphosurans, whose lateral eyes comprise a cuticle with a smooth outer surface and an inner one providing regular arrays of lens cylinders. This account discusses whether these disparate eye types speak for or against divergence from one ancestral eye type. Previous considerations of eye evolution, focusing on the eyes of trilobites and on facet proliferation in xiphosurans and myriapods, have proposed that the mode of development of eyes in those taxa is distinct from that of pancrustaceans and is the plesiomorphic condition from which facetted eyes have evolved. But the recent discovery of enormous regularly facetted compound eyes belonging to early Cambrian radiodontans suggests that high-resolution facetted eyes with superior optics may be the ground pattern organization for arthropods, predating the evolution of arthrodization and jointed post-protocerebral appendages. Here we provide evidence that compound eye organization in stem-group euarthropods of the Cambrian can be understood in terms of eye morphologies diverging from this ancestral radiodontan-type ground pattern. We show that in certain Cambrian groups apposition eyes relate to fixed or mobile eyestalks, whereas other groups reveal concomitant evolution of sessile eyes equipped with optics typical of extant xiphosurans. Observations of fossil material, including that of trilobites and eurypterids, support the proposition that the ancestral compound eye was the apposition type. Cambrian arthropods include possible precursors of mandibulate eyes. The latter are the modified compound eyes, now sessile, and their underlying optic lobes exemplified by scutigeromorph chilopods, and the mobile stalked compound eyes and more elaborate optic lobes typifying Pancrustacea. Radical divergence from an ancestral apposition type is demonstrated by the evolution of chelicerate eyes, from doublet sessile-eyed stem-group taxa to special apposition eyes of xiphosurans, the compound eyes of eurypterids, and single-lens eyes of arachnids. Different eye types are discussed with respect to possible modes of life of the extinct species that possessed them, comparing these to extant counterparts and the types of visual centers the eyes might have served.

Rapid, Reversible, Solid-Gas and Solution-Phase Insertion of CO2 into In-P Bonds.

The P,P-chelated heteroleptic complex bis[bis(diisopropylphosphino)amido]indium chloride [(i-Pr2P)2N]2InCl was prepared in high yield by treating InCl3 with 2 equiv of (i-Pr2P)2NLi in Et2O/tetrahydrofuran solution. Samples of [(i-Pr2P)2N]2InCl in a pentane slurry, a CH2Cl2 solution, or in the solid state were exposed to CO2, resulting in the insertion of CO2 into two of the four M-P bonds to produce [O2CP(i-Pr2)NP(i-Pr2)]2InCl in each case. Compounds were characterized by multinuclear NMR and IR spectroscopy, as well as single-crystal X-ray diffraction. ReactIR solution studies show that the reaction is complete in less than 1 min at room temperature in solution and in less than 2 h in the solid-gas reaction. The CO2 complex is stable up to at least 60 °C under vacuum, but the starting material is regenerated with concomitant loss of carbon dioxide upon heating above 75 °C. The compound [(i-Pr2P)2N]2InCl also reacts with CS2 to give a complicated mixture of products, one of which was identified as the CS2 cleavage product [S═P(i-Pr2)NP(i-Pr2)]2InCl]2(µ-Cl)[µ-(i-Pr2P)2N)].