An improved synthesis of 1-phenylpentafluoropropenes

1-Phenylpentafluoropropene and a number of its para- and ortho-substituted derivatives were prepared in high yields by reaction of hexafluoropropene with etheral solutions of corresponding phenylmagnesium bromides in sealed glass tubes under autogenous pressure. The products were obtained as mixtures of the Z and E isomers, which ratios varied from 1/2 to 1/6 in favour of the E forms. ¹⁹F n.m.r. and i.r. spectra and b.p. of the 1-phenylpentafluoropropenes are reported.     

Synthetic utility of 3-(perfluoro-1,1-dimethylbutyl)-1-propene. Part IV. Synthesis and properties of 1,1,1,2,2,3,3,8,9,9,9-undecafluoro-4,4,8-tris(trifluoromethyl)nonane - a new potential oxygen carrier for biomedical use

The title compound, CF₃CF₂CF₂(CF₃)₂CCH₂CH₂CH₂CF(CF₃)₂, was synthesised in high yield by a free radical addition of heptafluoroisopropyl iodide to 3-(perfluoro-1, 1-dimethylbutyl)-1- propene followed by reduction of the adduct. Physical properties and solubilities for oxygen, nitrogen, carbon dioxide and air of the new fluorohydrocarbon have been determined.     

Preparation of some highly halogenated derivative of furan

Direct chlorination of 2-(2H-hexafluoropropyl)-tetra- hydrofuran $\text{1}$ gave high yield of 2-(2-chlorohexafluoropropyl)- pentachloro-2,5-dihydrofuran $\text{2}$. Bromination of $\text{1}$ gave very complex mixture of products, from which three compounds, $\text{viz}$. 2-bromo-5-(2H-hexafluoropropyl)-furan $\text{3}$, 3-bromo-5-(2H-hexafluoropropyl)-furan $\text{4}$, and 2,4-dibromo-5-(2H-hexafluoropropyl)furan $\text{5}$ were isolated. Exchange fluorination of $\text{2}$ with dry KF at 240 – 300° led to a stepwise substitution of fluorines for chlorines to give mixtures of chloro-fluoro-2-(2-chlorohexafluoropropyl)-dihydrofurans $\text{7}$,$\text{8}$,$\text{9}$ and $\text{10}$, together with small amounts of 2-(2-chlorohexafluoropropyl)-3,4,5-trichlorofuran $\text{6}$.Exchange fluorination of 3,4-dihalo-2,2,5,5-tetrafluoro- 2,5-dihydrofurans $\text{11a}$ and $\text{11b}$ led to a substitution of fluorine for one vinylic halogen to give 3-halo-2,2,4,5,5-pentafluoro-2,5-dihydrofurans $\text{12a}$ and $\text{12b}$ in good yields.Compounds $\text{2}$ – $\text{12}$ were characterised by n.m.r., m.s., and i.r. spectroscopy and elemental analysis.     

Peptide mimotopes of phomopsins: Identification, characterization and application in an immunoassay

Peptide mimotopes of plant-associated toxins offer the potential for improving analytical and diagnostic methodologies as well as providing candidates for potential protective vaccines against plant poisoning diseases. Monoclonal antibody (mAb) C₃C₁₁, which recognizes the antimicrotubule phomopsin mycotoxins, was used to isolate peptide mimics of phomopsin A from a random 15-mer phage display peptide library. A total of 46 clones were isolated that showed specific reactivity with the mAb. Amino acid sequence analysis revealed four different types of mimotope sequences, all of which contained a common motif V-A-L/V-C. Of the 46 clones isolated, 44 contained the motif V-A-L-C while 2 contained the V-A-V-C motif. All four types of phage clones inhibited the reactivity of the mAb with phomopsin A in a competition ELISA. The clone with the mimotope sequence CT VALCNMYFGAKLD demonstrated the strongest binding. It was further shown that synthetic peptides containing these mimotope amino acid sequences were able to inhibit the mAb-phomopsin A interaction, indicating that the peptide mimotopes were responsible for the specific binding, independent of the phage framework. The results also suggest that the mimotope peptides bind to mAb C₃C₁₁ at the same site as phomopsin A. The application of recombinant phage particles carrying phomopsin mimotopes in immunoassay was evaluated and the results demonstrated approximately 100-fold increase in sensitivity in comparison with a conventional immunoassay using a chemically linked phomopsin-horseradish peroxidase conjugate.     

Fiber-optic sensing of high static pressure

Abstract

This paper describes a new fiber-optic sensor for pressures up to 200 MPa, based on the effect of hydrostatic stress on the polarization-mode coupling which occurs in highly birefringent fibers. Sensor construction, measurement set-up and typical output are presented. Results show that this new sensor displays far greater sensitivity when compared to solid-state pressure sensors.     

An Improved Synthesis of Dihalopyromellitic Acids

A practical molar scale syntheses of the commercially unavailable dichloro- and dibromopyromellitic acids are described in detail.     

Structural originations of irreversible capacity loss from highly lithiated copper oxides

We use electrochemistry, high-energy X-ray diffraction (XRD) with pair-distribution function analysis (PDF), and density functional theory (DFT) to study the instabilities of Li₂CuO₂ at varying state of charge. Rietveld refinement of XRD patterns revealed phase evolution from pure Li₂CuO₂ body-centered orthorhombic (Immm) space group to multiphase compositions after cycling. The PDF showed CuO₄ square chains with varying packing during electrochemical cycling. Peaks in the G(r) at the Cu-O distance for delithiated, LiCuO₂, showed CuO₄ square chains with reduced ionic radius for Cu in the 3+ state. At full depth of discharge to 1.5 V, CuO was observed in fractions greater than the initial impurity level which strongly affects the reversibility of the lithiation reactions contributing to capacity loss. DFT calculations showed electron removal from Cu and O during delithiation of Li₂CuO₂.     

Elastic heterogeneity in metallic glasses

When a stress is applied on a metallic glass it deforms following Hook's law. Therefore it may appear obvious that a metallic glass deforms elastically. Using x-ray diffraction and anisotropic pair-density function analysis we show that only about 3/4 in volume fraction of metallic glasses deforms elastically, whereas the rest of the volume is anelastic and in the experimental time scale deform without resistance. We suggest that this anelastic portion represents residual liquidity in the glassy state. Many theories, such as the free-volume theory, assume the density of defects in the glassy state to be of the order of 1%, but this result shows that it is as much as a quarter.     

Designing man–machine interactions for mobile clinical systems: MET triage support using Palm handhelds

The Mobile Emergency Triage (MET) system is a clinical triage support system that aids physicians in making triage decisions as to whether a child presenting in the Emergency Department of a hospital with a specific pain complaint should be discharged to a family physician, needs to be admitted for further investigation/observation, or requires an urgent specialist consult. The system’s mobile component is designed to work on handheld computers. This paper presents our experience and discusses our original solutions with regard to designing man–machine interactions for mobile clinical support systems. The specific interactions adopted in the MET design that are discussed in the paper were created in consultation with potential end-users and tested at the Children’s Hospital of Eastern Ontario in Ottawa.