Modelling of a novel high-impedance matching layer for high frequency (>30 MHz) ultrasonic transducers

This work describes a new approach to impedance matching for ultrasonic transducers. A single matching layer with high acoustic impedance of 16 MRayls is demonstrated to show a bandwidth of around 70%, compared with conventional single matching layer designs of around 50%. Although as a consequence of this improvement in bandwidth, there is a loss in sensitivity, this is found to be similar to an equivalent double matching layer design. Designs are calculated by using the KLM model and are then verified by FEA simulation, with very good agreement Considering the fabrication difficulties encountered in creating a high-frequency double matched design due to the requirement for materials with specific acoustic impedances, the need to accurately control the thickness of layers, and the relatively narrow bandwidths available for conventional single matched designs, the new approach shows advantages in that alternative (and perhaps more practical) materials become available, and offers a bandwidth close to that of a double layer design with the simplicity of a single layer design. The disadvantage is a trade-off in sensitivity. A typical example of a piezoceramic transducer matched to water can give a 70% fractional bandwidth (comparable to an ideal double matched design of 72%) with a 3 dB penalty in insertion loss.     

The Reduction of Aromatic Aldehydes and Benzils by Sodium Formaldehyde Sulphoxylate

Sodium formaldehyde sulphoxylate is shown to be an effective reagent for the reduction of some aromatic aldehydes to alcohols. Benzils are also reduced under neutral or basic conditions to give mainly benzoins. Ketones are reduced only slowly.     

Identification of ligands that target the HCV-E2 binding site on CD81

Hepatitis C is a global health problem. While many drug companies have active R&D efforts to develop new drugs for treating Hepatitis C virus (HCV), most target the viral enzymes. The HCV glycoprotein E2 has been shown to play an essential role in hepatocyte invasion by binding to CD81 and other cell surface receptors. This paper describes the use of AutoDock to identify ligand binding sites on the large extracellular loop of the open conformation of CD81 and to perform virtual screening runs to identify sets of small molecule ligands predicted to bind to two of these sites. The best sites selected by AutoLigand were located in regions identified by mutational studies to be the site of E2 binding. Thirty-six ligands predicted by AutoDock to bind to these sites were subsequently tested experimentally to determine if they bound to CD81-LEL. Binding assays conducted using surface Plasmon resonance revealed that 26 out of 36 (72 %) of the ligands bound in vitro to the recombinant CD81-LEL protein. Competition experiments performed using dual polarization interferometry showed that one of the ligands predicted to bind to the large cleft between the C and D helices was also effective in blocking E2 binding to CD81-LEL.     

The Fourier space restricted Hartree-Fock method for the electronic structure calculation of linear poly(tetrafluoroethylene)

Building on the pioneering work of Jean-Marie André and working in the laboratory he founded, the authors have developed a code called FT-1D to make Hartree-Fock electronic structure computations for stereoregular polymers using Ewald-type convergence acceleration methods. That code also takes full advantage of all line-group symmetries to calculate only the minimal set of two-electron integrals and to optimize the computation of the Fock matrix. The present communication reports a benchmark study of the FT-1D code using polytetrafluoroethylene(PTFE) as a test case. Our results not only confirm the algorithmic correctness of the code through agreement with other studies where they are applicable, but also show that the use of convergence acceleration enables accurate results to be obtained in situations where other widely-used codes(e.g., PLH and Crystal) fail. It is also found that full attention to the line-group symmetry of the PTFE polymer leads to an increase of between one and two orders of magnitude in the speed of computation. The new code can therefore be viewed as extending the range of electronic-structure computations for stereoregular polymers beyond the present scope of the successful and valuable code Crystal.     

Simulations of ferrite-dielectric-wire composite negative index materials

We perform extensive finite difference time domain simulations of ferrite based negative index of refraction composites. A wire grid is employed to provide negative permittivity. The ferrite and wire grid interact to provide both negative and positive index of refraction transmission peaks in the vicinity of the ferrite resonance. Notwithstanding the extreme anisotropy in the index of refraction of the composite, negative refraction is seen at the composite air interface allowing the construction of a focusing concave lens with a magnetically tunable focal length.     

Comparative 11A structure of two molluscan hemocyanins from 3D cryo-electron microscopy

Hemocyanins are giant extracellular proteins that transport oxygen in the hemolymph of many molluscs. Molluscan hemocyanins are cylindrical decamers or didecamers of a 350-400 kDa subunit that contains seven or eight different covalently linked globular functional units (FUs), arranged in a linear manner. Each FU carries a single copper active site and reversibly binds one dioxygen molecule. As a consequence, the decamer can carry up to 70 or 80 O(2) molecules. Although complete sequence information is now available from several molluscan hemocyanins, many details of the quaternary structure are still unclear, including the topology of the 10 subunits within the decamer. Here we show 3D reconstructions from cryo-electron micrographs of the hemocyanin decamer of Nautilus pompilius (Cephalopoda) and Haliotis tuberculata (Gastropoda) at a resolution of 11A (FSC(1/2-bit) criterion). The wall structure of both hemocyanins is very similar and shows, as in previous reconstructions, three tiers with 20 functional units each that encircle the cylinder wall, and the 10 oblique minor and major wall grooves. However, the six types of wall FUs of the polypeptide subunit, termed a-b-c-d-e-f, are now for the first time individually discernable by their specific orientation, shape, and connections. Also, the internal collar complex of the decamers shows superior resolution which, in this case, reveals striking differences between the two hemocyanins. The five arcs (FU-g pairs) of the central collar (in both hemocyanins) and the five slabs (FU-h pairs) of the peripheral collar (only present in Haliotis hemocyanin), as well as their connections to the wall and to each other are now more clearly defined. The arc is attached to the wall through a feature termed the anchor, a previously undescribed structural element of the hemocyanin wall.     

Synthesis and Biological Evaluation of a Class of Mitochondrially‐Targeted Gadolinium(III) Agents

A structure–activity relationship study of a library of novel bifunctional Gd^III complexes covalently linked to arylphosphonium cations is reported. Such complexes have been designed for potential application in binary cancer therapies such as neutron capture therapy and photon activation therapy. A positive correlation was found between lipophilicity and cytotoxicity of the complexes. Mitochondria uptake was determined by means of inductively coupled plasma mass spectrometry (ICP‐MS), and Gd uptake was determined by means of quantification using synchrotron X‐ray fluorescence (XRF) imaging. A negative correlation between lipophilicity and tumour selectivity of the Gd^III complexes was demonstrated. This study highlights the delicate balance required to minimise in vitro cytotoxicity and optimise in vitro tumour selectivity and mitochondrial localisation for this new class of mitochondrially‐targeted binary therapy agents. We also report the highest in vitro tumour selectivity for any Gd agent reported to date, with a T/N (tumour/normal cell) ratio of up to 23.5±6.6.     

Synthesis,Structure, and Reactivity of a Gold Carbenoid Complex That Lacks Heteroatom Stabilization

Hydride abstraction from the neutral gold cycloheptatrienyl complex [( P )Au(η¹‐C₇H₇)] ( P =P(tBu)₂(o‐biphenyl)) with triphenylcarbenium tetrafluoroborate at ?80 °C led to the isolation of the cationic gold cycloheptatrienylidene complex [( P )Au(η¹‐C₇H₆)]⁺ BF₄^? in 52 % yield, which was characterized in solution and by single‐crystal X‐ray diffraction. This cycloheptatrienylidene complex represents the first example of a gold carbenoid complex that lacks conjugated heteroatom stabilization of the electron‐deficient C1 carbon atom. The cycloheptatrienylidene ligand of this complex is reactive; it can be reduced by mild hydride donors, and converted to tropone in the presence of pyridine N‐oxide.     

Comparative study of free energies of solvation of phenylimidazole inhibitors of cytochrome P450cam by free energy simulation,AMSOL, and Poisson Boltzmann methods

Free energies of solvation of phenylimidazole inhibitors of cytochrome P450cam were determined using (1) free energy simulation, (2) AMSOL-SM2 semiempirical methods, and (3) Poisson-Boltzmann methods. The goals of this study were threefold: (1) to compare the results obtained from the three different methods, (2) to investigate the effect of inclusion of intraperturbed group interactions on free energy simulation estimates of solvation free energy differences, and (3) to investigate to what extent differences in free energies of solvation among three of these inhibitors could account for observed differences in their enzyme binding free energies. In general, relative solvation free energies obtained from the free energy simulations and AMSOL-SM2 methods give comparable results (i.e., the same rank ordering and similar quantitative results, differing significantly from results obtained using Poisson-Boltzmann methods). The free energy simulation studies suggest that the neglect of intraperturbed group interactions had little effect on rank order of free energies of solvation of the polar phenylimidazoles. The relative desolvation free energies of the three inhibitors of P450cam—1-phenylimidazole (1-PI), 2-phenylimidazole (2-PI), and 4-phenylimidazole (4-PI)—with known enzyme bound X-ray structures parallel that of their known binding affinities and could account for most of the differences in the free energies of binding of these three inhibitors to P450cam. The origin of the difference of the free energies of solution of these three inhibitors is primarily the additional interaction between solvent and N(SINGLE BOND)H group in the imidazole ring of 2- and 4-phenylimidazole that is absent in the 1-phenylimidazole isomer. This hypothesis is substantiated by a second comparison of the relative solvation free energies of 4-phenylimidazole with its methylated derivative, 3-methyl-4-phenylimidazole, also lacking an N(SINGLE BOND)H group. © 1996 by John Wiley & Sons, Inc.