A Solid-State 11B NMR and Computational Study of Boron Electric Field Gradient and Chemical Shift Tensors in Boronic Acids and Boronic Esters

The results of a solid-state 11B NMR study of a series of 10 boronic acids and boronic esters with aromatic substituents are reported. Boron-11 electric field gradient (EFG) and chemical shift (CS) tensors obtained from analyses of spectra acquired in magnetic fields of 9.4 and 21.1 T are demonstrated to be useful for gaining insight into the molecular and electronic structure about the boron nucleus. Data collected at 21.1 T clearly show the effects of chemical shift anisotropy (CSA), with tensor spans (Ω) on the order of 10−40 ppm. Signal enhancements of up to 2.95 were achieved with a DFS-modified QCPMG pulse sequence. To understand the relationship between the measured tensors and the local structure better, calculations of the 11B EFG and magnetic shielding tensors for these compounds were conducted. The best agreement was found between experimental results and those obtained from GGA revPBE DFT calculations. A positive correlation was found between Ω and the dihedral angle (CCBO), which describes the orientation of the boronic acid/ester functional group relative to an aromatic system bound to boron. The small boron CSA is discussed in terms of paramagnetic shielding contributions as well as diamagnetic shielding contributions. Although there is a region of overlap, both Ω and the 11B quadrupolar coupling constants tend to be larger for boronic acids than for the esters. We conclude that the span is generally the most characteristic boron NMR parameter of the molecular and electronic environment for boronic acids and esters, and show that the values result from a delicate interplay of several competing factors, including hydrogen bonding, the value of CCBO, and the electron-donating or withdrawing substituents bound to the aromatic ring.Natural Sciences and Engineering Research Council (NSERC) of Canada and the Canada Foundation for Innovation

A study of the thermal degradation of glass fibre sizings at composite processing temperatures

Although not fully understood, it is well recognized that optimal working of glass fibre sizings is necessary to maximize the performance of glass fibre reinforced polymer composites. It is important that the organic components in such sizings continue to function after exposure to the high temperatures often experienced during composite processing. This study presents the results on the thermal stability of polypropylene and epoxy compatible glass fibre sizings obtained using TGA, microbond adhesion measurement and composite mechanical testing. Test results indicate that the performance of commercial polypropylene compatible glass fibre sizings can be significantly compromised by thermo-oxidative degradation at normal composite processing temperatures. A significant reduction in composite performance is directly related to a loss of fibre-matrix adhesion caused by thermal degradation of some of the principal sizing components

First Record of Nestling Relocation by Adult Gyrfalcons (\u3cem\u3eFalco rusticolus\u3c/em\u3e) Following Nest Collapse

Nest collapse has been documented in many bird species, with little discussion of adult behavior following collapse. We present evidence of a partial collapse of a Gyrfalcon (Falco rusticolus) nest during the nestling period and the subsequent adult response. A nest camera captured the nest collapse and showed one adult Gyrfalcon holding a live nestling in its beak before leaving the nest. Later, we found the surviving nestling alive in an alternate nest 5 m from the original nest, presumably transported there by the adult. We believe this is the first report of an adult Gyrfalcon moving a nestling to a new location following nest disturbance. We place this observation into a context of Gyrfalcon nesting behavior described in published sources. The continued use of nest cameras may provide additional documentation and insight into this behavior and its prevalence in birds

Multinuclear Solid-State Magnetic Resonance as a Sensitive Probe of Structural Changes upon the Occurrence of Halogen Bonding in Co-crystals

Although the understanding of intermolecular interactions, such as hydrogen bonding, is relatively well-developed, many additional weak interactions work both in tandem and competitively to stabilize a given crystal structure. Due to a wide array of potential applications, a substantial effort has been invested in understanding the halogen bond. Here, we explore the utility of multinuclear (13C, 14/15N, 19F, and 127I) solid-state magnetic resonance experiments in characterizing the electronic and structural changes which take place upon the formation of five halogen-bonded co-crystalline product materials. Single-crystal X-ray diffraction (XRD) structures of three novel co-crystals which exhibit a 1:1 stoichiometry between decamethonium diiodide (i.e., [(CH3)3N+(CH 2)10N+(CH3)3][2 I -]) and different para-dihalogen-substituted benzene moieties (i.e., p-C6X2Y4, X=Br, I; Y=H, F) are presented. 13C and 15N NMR experiments carried out on these and related systems validate sample purity, but also serve as indirect probes of the formation of a halogen bond in the co-crystal complexes in the solid state. Long-range changes in the electronic environment, which manifest through changes in the electric field gradient (EFG) tensor, are quantitatively measured using 14N NMR spectroscopy, with a systematic decrease in the 14N quadrupolar coupling constant (CQ) observed upon halogen bond formation. Attempts at 127I solid-state NMR spectroscopy experiments are presented and variable-temperature 19F NMR experiments are used to distinguish between dynamic and static disorder in selected product materials, which could not be conclusively established using solely XRD. Quantum chemical calculations using the gauge-including projector augmented-wave (GIPAW) or relativistic zeroth-order regular approximation (ZORA) density functional theory (DFT) approaches complement the experimental NMR measurements and provide theoretical corroboration for the changes in NMR parameters observed upon the formation of a halogen bond

Search for Rayleigh scattering in the atmosphere of GJ1214b

We investigate the atmosphere of GJ1214b, a transiting super-Earth planet with a low mean density, by measuring its transit depth as a function of wavelength in the blue optical portion of the spectrum. It is thought that this planet is either a mini-Neptune, consisting of a rocky core with a thick, hydrogen-rich atmosphere, or a planet with a composition dominated by water. Most observations favor a water-dominated atmosphere with a small scale-height, however, some observations indicate that GJ1214b could have an extended atmosphere with a cloud layer muting the molecular features. In an atmosphere with a large scale-height, Rayleigh scattering at blue wavelengths is likely to cause a measurable increase in the apparent size of the planet towards the blue. We observed the transit of GJ1214b in the B-band with the FOcal Reducing Spectrograph (FORS) at the Very Large Telescope (VLT) and in the g-band with both ACAM on the William Hershel Telescope (WHT) and the Wide Field Camera (WFC) at the Isaac Newton Telescope (INT). We find a planet-to-star radius ratio in the B-band of 0.1162+/-0.0017, and in the g-band 0.1180+/-0.0009 and 0.1174+/-0.0017 for the WHT & INT observations respectively. These optical data do not show significant deviations from previous measurements at longer wavelengths. In fact, a flat transmission spectrum across all wavelengths best describes the combined observations. When atmospheric models are considered a small scale-height water-dominated model fits the data best.Comment: Accepted for publication in Ap

Micro-mechanical investigation of glass fibre/resin interface failure in mode I and mode II

Fibre reinforced composites are experiencing a period of consistent and significant growth which is predicted to continue, due to the sustained global increase in demand across a number of industrial sectors. One of the critical elements in the success of such composites in both the short and longer term is the interface/interphase between reinforcement fibres and matrix. Poor adhesion will generally lead to composites with insufficient mechanical performance. Degradation of the interface/interphase region during service life will lead to a decrease in performance, eventually to a point where the part can no longer fulfil its intended function. Micro-mechanical test methods can be an advantageous approach to analysing the fibre-matrix interface as they reduce material consumption and simplify the analysis compared with composites. In this paper some of the disadvantages of the commonly used microbond test are discussed, particularly difficulties related to testing of vinyl esters. A new micro-mechanical interface test is introduced which induces failure at the interface in mode I as opposed to the shear failure that occurs with microbond and several other contemporary interface tests

A malaria vaccine candidate based on an epitope of the Plasmodium falciparum RH5 protein

BACKGROUND: The Plasmodium falciparum protein RH5 is an adhesin molecule essential for parasite invasion of erythrocytes. Recent studies show that anti-PfRH5 sera have potent invasion-inhibiting activities, supporting the idea that the PfRH5 antigen could form the basis of a vaccine. Therefore, epitopes recognized by neutralizing anti-PfRH5 antibodies could themselves be effective vaccine immunogens if presented in a sufficiently immunogenic fashion. However, the exact regions within PfRH5 that are targets of this invasion-inhibitory activity have yet to be identified. METHODS: A battery of anti-RH5 monoclonal antibodies (mAbs) were produced and screened for their potency by inhibition of invasion assays in vitro. Using an anti-RH5 mAb that completely inhibited invasion as the selecting mAb, affinity-selection using random sequence peptide libraries displayed on virus-like particles of bacteriophage MS2 (MS2 VLPs) was performed. VLPs were sequenced to identify the specific peptide epitopes they encoded and used to raise specific antisera that was in turn tested for inhibition of invasion. RESULTS: Three anti-RH5 monoclonals (0.1 mg/mL) were able to inhibit invasion in vitro by >95%. Affinity-selection with one of these mAbs yielded a VLP which yielded a peptide whose sequence is identical to a portion of PfRH5 itself. The VLP displaying the peptide binds strongly to the antibody, and in immunized animals elicits an anti-PfRH5 antibody response. The resulting antisera against the specific VLP inhibit parasite invasion of erythrocytes more than 90% in vitro. CONCLUSIONS: Here, data is presented from an anti-PfRH5 mAb that completely inhibits erythrocyte invasion by parasites in vitro, one of the few anti-malarial monoclonal antibodies reported to date that completely inhibits invasion with such potency, adding to other studies that highlight the potential of PfRH5 as a vaccine antigen. The specific neutralization sensitive epitope within RH5 has been identified, and antibodies against this epitope also elicit high anti-invasion activity, suggesting this epitope could form the basis of an effective vaccine against malaria

The targeted delivery of multicomponent cargos to cancer cells by nanoporous particle-supported lipid bilayers.

Encapsulation of drugs within nanocarriers that selectively target malignant cells promises to mitigate side effects of conventional chemotherapy and to enable delivery of the unique drug combinations needed for personalized medicine. To realize this potential, however, targeted nanocarriers must simultaneously overcome multiple challenges, including specificity, stability and a high capacity for disparate cargos. Here we report porous nanoparticle-supported lipid bilayers (protocells) that synergistically combine properties of liposomes and nanoporous particles. Protocells modified with a targeting peptide that binds to human hepatocellular carcinoma exhibit a 10,000-fold greater affinity for human hepatocellular carcinoma than for hepatocytes, endothelial cells or immune cells. Furthermore, protocells can be loaded with combinations of therapeutic (drugs, small interfering RNA and toxins) and diagnostic (quantum dots) agents and modified to promote endosomal escape and nuclear accumulation of selected cargos. The enormous capacity of the high-surface-area nanoporous core combined with the enhanced targeting efficacy enabled by the fluid supported lipid bilayer enable a single protocell loaded with a drug cocktail to kill a drug-resistant human hepatocellular carcinoma cell, representing a 10(6)-fold improvement over comparable liposomes

π‐complexes of diborynes with main group atoms

We present herein an in‐depth study of complexes in which a molecule containing a boron‐boron triple bond is bound to tellurate cations. The analysis allows the description of these salts as true π complexes between the B−B triple bond and the tellurium center. These complexes thus extend the well‐known Dewar‐Chatt‐Duncanson model of bonding to compounds made up solely of p block elements. Structural, spectroscopic and computational evidence is offered to argue that a set of recently reported heterocycles consisting of phenyltellurium cations complexed to diborynes bear all the hallmarks of π‐complexes in the π‐complex/metallacycle continuum envisioned by Joseph Chatt. Described as such, these compounds are unique in representing the extreme of a metal‐free continuum with conventional unsaturated three-membered rings (cyclopropenes, azirenes, borirenes) occupying the opposite end