Molecular dynamics results for the radial distribution functions of highly asymmetric hard sphere mixtures

Molecular dynamics (MD) results for the radial distribution functions of mixtures of large and small hard spheres are reported for size ratios whose (large/small) values are 1, 2.5, 5, 7.5, and 10 in the region where the concentration of the large spheres is very small. The MD contact values of these functions are compared with formulae due to Boublik, Mansoori, Carnahan, Starling, Leland, Grundke, and Henderson, Viduna and Smith, Henderson, Trokhymchuk, Woodcock, and Chan, as well as new formulae that are considered here. The new formulae give good agreement for the large–small contact values and reasonably good agreement for the large–large contact values. The Viduna–Smith formula is satisfactory for the small–small contact value and quite reasonable for the small–large contact value. Undoubtedly, further improvements are possible. These results give insight into what may be called the colloidal limit, where the size ratio is exceedingly large while the concentration of the large spheres is exceedingly small, and into the passage to this limit.     

Plasmonic finite-thickness metal–semiconductor–metal waveguide as ultra-compact modulator

We propose a plasmonic waveguide with semiconductor gain material for optoelectronic integrated circuits. We analyze properties of a finite-thickness metal–semiconductor–metal (F-MSM) waveguide to be utilized as an ultra-compact and fast plasmonic modulator. The InP-based semiconductor core allows electrical control of signal propagation. By pumping the core we can vary the gain level and thus the transmittance of the whole system. The study of the device was made using both analytical approaches for planar two-dimensional case as well as numerical simulations for finite-width waveguides. We analyze the eigenmodes of the F-MSM waveguide, propagation constant, confinement factor, Purcell factor, absorption coefficient, and extinction ratio of the structure. We show that using thin metal layers instead of thick ones we can obtain higher extinction ratio of the device.     

Transition absorption as a mechanism of surface photoelectron emission from metals

Transition absorption of a photon by an electron passing through a boundary between two media with different permittivities is described both classically and quantum mechanically. Transition absorption is shown to make a substantial contribution to photoelectron emission at a metal/semicon‐ductor interface in nanoplasmonic systems, and is put forth as a possible microscopic mechanism of the surface photoelectric effect in photodetectors and solar cells containing plasmonic nanoparticles.

     

Plasmonic modulator based on gain-assisted metal–semiconductor–metal waveguide

We investigate plasmonic modulators with gain material to be implemented as ultra-compact and ultra-fast active nanodevices in photonic integrated circuits. We analyze metal–semiconductor–metal (MSM) waveguides with InGaAsP-based active material layers as ultra-compact plasmonic modulators. The modulation is performed by changing the gain of the core, that results in different transmittance through the waveguides. A MSM waveguide enables high field localization and therefore high modulation speed. Bulk semiconductor, quantum wells and quantum dots, arranged in either horizontal or vertical layout, are considered as the core of the MSM waveguide. Dependences on the waveguide core size and gain values of various active materials are studied. The designs consider also practical aspects like n- and p-doped layers and barriers in order to obtain close to reality results. The effective propagation constants in the MSM waveguides are calculated numerically. Their changes in the switching process are considered as a figure of merit. We show that a MSM waveguide with electrical current control of the gain incorporates compactness and deep modulation along with having a reasonable level of transmittance.     

Nonconcerted cycloaddition of 2H-azirines to acylketenes: a route to N-bridgehead heterocycles

Reactions of acylketenes, generated from diazo diketones, with 2-unsubstituted and 2-monosubstituted 3-aryl-2H-azirines lead to 1:1 or 2:1 adducts, which are derivatives of 5-oxa-1-azabicyclo[4.1.0]hept-3-ene or 5,7-dioxa-1-azabicyclo[4.4.1]undeca-3,8-diene. According to DFT B3LYP/6-31G(d) computations, the formation of (4+2)-monoadducts proceeds via a stepwise non-pericyclic mechanism. Reaction with methanol transforms quantitatively both 1:1 and 2:1 adducts into 1,4-oxazepine derivatives.     

On Nuclei and Duals of Semifields of Order q 4, q is a Power of 2

The aim of this article is to investigate the nuclei of a semifield A of order q ⁴, q is a power of 2, admitting a four-group E of automorphisms isomorphic to Z ₂ × Z ₂ acting freely on A and having GF(q ²) in its left nucleus. We also study the dual semifield A* of A and show that A and A* are isomorphic.     

Template directed synthesis of antibody Fc conjugates with concomitant ligand release

Antibodies are an attractive therapeutic modality for cancer treatment as they allow the increase of the treatment response rate and avoid the severe side effects of chemotherapy. Notwithstanding the strong benefit of antibodies, the efficacy of anti-cancer antibodies can dramatically vary among patients and ultimately result in no response to the treatment. Here, we have developed a novel means to regioselectively label the Fc domain of any therapeutic antibody with a radionuclide chelator in a single step chemistry, with the aim to study by SPECT/CT imaging if the radiolabeled antibody is capable of targeting cancer cells in vivo. A Fc-III peptide was used as bait to bring a carbonate electrophilic site linked to a metal chelator and to a carboxyphenyl leaving group in close proximity with an antibody Fc nucleophile amino acid (K317), thereby triggering the covalent linkage of the chelator to the antibody lysine, with the concomitant release of the carboxyphenyl Fc-III ligand. Using CHX-A′′-DTPA, we radiolabeled trastuzumab with indium-111 and showed in biodistribution and imaging experiments that the antibody accumulated successfully in the SK-OV-3 xenograft tumour implanted in mice. We found that our methodology leads to homogeneous conjugation of CHX-A′′-DTPA to the antibody, and confirmed that the Fc domain can be selectively labeled at K317, with a minor level of unspecific labeling on the Fab domain. The present method can be developed as a clinical diagnostic tool to predict the success of the therapy. Furthermore, our Fc-III one step chemistry concept paves the way to a broad array of other applications in antibody bioengineering.

A method is reported to attach a radionuclide chelator in a single step chemistry to the Fc domain of any therapeutic antibody.     

Cucurbit[6]uril Hyperpolarized Chemical Exchange Saturation Transfer Pulse Sequence Parameter Optimization and Detectability Limit Assessment at 3.0T

Molecular imaging is the future of personalized medicine; however, it requires effective contrast agents. Hyperpolarized chemical exchange saturation transfer (HyperCEST) can boost the signal of Hyperpolarized ¹²⁹Xe MRI and render it a molecular imaging modality of high efficiency. Cucurbit[6]uril (CB6) has been successfully employed in vivo as a contrast agent for HyperCEST MRI, however its performance in a clinical MRI scanner has yet to be optimized. In this study, MRI pulse sequence parameter optimization was first performed in CB6 solutions in phosphate-buffered saline (PBS), and subsequently in whole sterile citrated bovine blood. The performance of four different depolarization pulse shapes (sinusoidal, 3-lobe sinc (3LS), rectangular (block), and hyperbolic secant (hypsec) was optimized. The detectability limits of CB6 in a clinical 3.0T MRI scanner was assessed using the optimized pulse sequences. The 3LS depolarization pulses performed best, and demonstrated 24 % depletion in a 25 μM solution of CB6 in PBS. It performed similarly in blood. The CB6 detectability limit was found to be 100 μM in citrated bovine blood with a correspondent HyperCEST depletion of 30 % ±9 %. For the first time, the HP ¹²⁹Xe HyperCEST effect was observed in red blood cells (RBC) and had a similar strength as HyperCEST in plasma.     

Detection of pyridaben residue levels in hot pepper fruit and leaves by liquid chromatography–tandem mass spectrometry: effect of household processes

Following quick, easy, cheap, effective, rugged and safe (QuEChERS) and LC/MS/MS analysis, pyridaben residual levels were determined in unprocessed and processed hot pepper fruit and leaves. The linearities were satisfactory with determination coefficients (R²) in excess of 0.995 in processed and unprocessed pepper fruit and leaves. Recoveries at various concentrations were 79.9–105.1% with relative standard deviations ≤15%. The limits of quantitation of 0.003–0.012 mg/kg were very low compared with the maximum residue limits (2–5 mg/kg) set by the Ministry of Food and Drug Safety, Republic of Korea. The effects of various household processes, including washing, blanching, frying and drying under different conditions (water volume, blanching time and temperature) on residual concentrations were evaluated. Both washing and blanching (in combination with high water volume and time factor) significantly reduced residue levels in hot pepper fruit and leaves compared with other processes. In sum, the developed method was satisfactory and could be used to accurately detect residues in unprocessed and processed pepper fruit and leaves. It is recommended that pepper fruit/leaves be blanched after washing before being consumed to protect consumers from the negative health effects of detected pesticide residues. Copyright © 2014 John Wiley & Sons, Ltd.     

Protein Delivery System Containing a Nickel‐Immobilized Polymer for Multimerization of Affinity‐Purified His‐Tagged Proteins Enhances Cytosolic Transfer

Recombinant proteins with cytosolic or nuclear activities are emerging as tools for interfering with cellular functions. Because such tools rely on vehicles for crossing the plasma membrane we developed a protein delivery system consisting in the assembly of pyridylthiourea‐grafted polyethylenimine (πPEI) with affinity‐purified His‐tagged proteins pre‐organized onto a nickel‐immobilized polymeric guide. The guide was prepared by functionalization of an ornithine polymer with nitrilotriacetic acid groups and shown to bind several His‐tagged proteins. Superstructures were visualized by electron and atomic force microscopy using 2 nm His‐tagged gold nanoparticles as probes. The whole system efficiently carried the green fluorescent protein, single‐chain antibodies or caspase 3, into the cytosol of living cells. Transduction of the protease caspase 3 induced apoptosis in two cancer cell lines, demonstrating that this new protein delivery method could be used to interfere with cellular functions.