Synthesis of an advanced intermediate en route to the mitomycin natural products

[Structure: see text] An advanced intermediate in our planned synthesis of mitomycin C has been acquired in nine steps from tert-butyl glyoxylate. The aziridinyl pyrrolidine and quinone subunits are coupled regioselectively to arrive at an enamine that is prepared for C10 homologation.     

Bimolecular radical termination: New perspectives and insights

The reversible addition‐fragmentation chain transfer‐chain length dependent termination (RAFT‐CLD‐T) method has allowed us to answer a number of fundamental questions regarding the mechanism of diffusion‐controlled bimolecular termination in free‐radical polymerization (FRP). We carried out RAFT‐mediated polymerizations of methyl acrylate (MA) in the presence of a star matrix to develop an understanding of the effect of polymer matrix architecture on the termination of linear polyMA radicals and compared this to polystyrene, polymethyl methacrylate, and polyvinyl acetate systems. It was found that the matrix architecture had little or no influence on termination in the dilute regime. However, due to the smaller hydrodynamic volumes of the stars in solution compared to linear polymer of the same molecular weight, the gel onset point occurred at greater conversions, and supported the postulate that chain overlap (or c*) is the main cause for the observed autoacceleration observed in FRP. Other theories based on “short–long” termination or free‐volume should be disregarded. Additionally, since our systems are well below the entanglement molecular weight, entanglements should also be disregarded as the cause of the gel onset. The semidilute regime occurs over a small conversion range and is difficult to quantify. However, we obtain accurate dependencies for termination in the concentrated regime, and observed that the star polymers (through the tethering of the arms) provided constriction points in the matrix that significantly slow the diffusion of linear polymeric radicals. Although, this could at first sight be postulated to be due to reptation, the dependencies showed that reptation could be considered only at very high conversions (close to the glass transition regime). In general, we find from our data that the polymer matrix is much more mobile than what is expected if reptation were to dominate. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3155–3173, 2008     

Ruthenium porphyrin functionalized single-walled carbon nanotube arrays--a step toward light harvesting antenna and multibit information storage

Ruthenium porphyrin functionalized single-walled carbon nanotube arrays have been prepared using coordination of the axial position of the metal ion onto 4-aminopyridine preassembled single-walled carbon nanotubes directly anchored to a silicon(100) surface (SWCNTs-Si). The formation of these ruthenium porphyrin functionalized single-walled carbon nanotube array electrodes (RuTPP-SWCNTs-Si) has been monitored using infrared spectroscopy (IR), differential pulse voltammetry (DPV), atomic force microscopy (AFM), laser desorption time-of-flight mass spectroscopy (LDI-TOF-MS), UV-vis spectroscopy, fluorescence spectroscopy, and cyclic voltammetry. Electrochemical results show two successive one-electron reversible redox waves. The surface concentration of the ruthenium porphyrin molecules is 3.44 x 10 (-8) mol cm (-2). Optical results indicate that the immobilization of ruthenium porphyrin enhances the light absorption of SWCNTs-Si surfaces in the visible light region. Moreover mixed assembly of ferrocene/porphyrin onto carbon nanotube arrays has been achieved by altering the ratio of two redox-active species in the deposition solution. These results suggest the ruthenium porphyrin modified electrodes are excellent candidates for molecular memory devices and light harvesting antennae.     

A diastereo- and enantioselective synthesis of alpha-substituted syn-alpha,beta-diamino acids

Highly diastereo- and enantioselective additions of substituted alpha-nitroesters to imines have been developed. High diastereoselection relies on the finding that the combination of chiral proton catalyst 2b and alpha-nitro aryl esters bearing 2,6-disubstitution combine to raise substrate-controlled diastereoselection to >20:1 in favor of the syn diastereomer. Furthermore, the chiral catalyst provides enantioselection to the 99% level through control of the addition step in which the azomethine pi-faces are differentiated. The bifunctional chiral protic acid catalyst enables these reactions to proceed without separate preactivation of either substrate, leading to a straightforward synthetic protocol for the formation of alpha,beta-diamino phenyl alanine derivatives.     

Emission Mössbauer spectroscopy study of fluence dependence of paramagnetic relaxation in Mn/Fe implanted ZnO

Emission Mössbauer Spectroscopy following the implantation of radioactive precursor isotope ⁵⁷Mn⁺ (T _1/2= 1.5 min) into ZnO single crystals at ISOLDE/CERN shows that a large fraction of ⁵⁷Fe atoms produced in the ⁵⁷Mn beta decay is created as paramagnetic Fe³⁺ with relatively long spin-lattice relaxation times. Here we report on ZnO pre-implanted with ⁵⁶Fe to fluences of 2×10¹³, 5×10 ¹³ and 8 × 10¹³ ions/cm² in order to investigate the dependence of the paramagnetic relaxation rate of Fe³⁺ on fluence. The spectra are dominated by magnetic features displaying paramagnetic relaxation effects. The extracted spin-lattice relaxation rates show a slight increase with increasing ion fluence at corresponding temperatures and the area fraction of Fe³⁺ at room temperature reaches a maximum contribution of 80(3)% in the studied fluence range.     

Inflammatory responses of a human keratinocyte cell line to 10 nm citrate- and PEG-coated silver nanoparticles

Silver nanoparticles (AgNPs) are among the most commonly used engineered NPs and various commercially available products are designed to come in direct contact with the skin (wound dressings, textiles, creams, among others). Currently, there is limited understanding of the influence of coatings on the toxicity of AgNPs and in particular their ability to impact on AgNP’s mediated inflammatory responses. As AgNPs are often stabilized by different coatings, including citrate and polyethyleneglycol (PEG), in this study we investigate the influence of citrate (Cit10) or PEG (PEG10) coatings to 10 nm AgNP on skin, using human HaCaT keratinocytes. AgNPs cytotoxicity and inflammatory response (nuclear factor (NF)-κB induction and cytokine production) of HaCaT were assessed after in vitro exposure to 10 and 40 µg/mL after 4, 24, and 48 h. Results showed that although both types of coated AgNPs decreased cell proliferation and viability, Cit10 AgNPs were more toxic. NF-κB inhibition was observed for the highest concentration (40 µg/mL) of PEG10 AgNPs, and the putative link to early apoptotic pathways observed in these cells is discussed. No production of IL-1β, IL-6, IL-10, and TNFα was stimulated by AgNPs. Furthermore, Cit10 and PEG10 AgNPs decreased the release of MCP-1 by HaCaT cells after 48 h of exposure. As cytokines are vital for the immunologic regulation in the human body, and it is demonstrated that they may interfere with NPs, more research is needed to understand how different AgNPs affect the immune system.     

Carbon-carbon bond forming reactions with substrates absorbed non-covalently on a cellulose chromatography paper support

Reactions and purifications, including carbon-carbon bond forming reactions, can be carried out on a cellulose support on which the substrates are non-covalently absorbed.     

Diffusion modeling of an HF argon plasma discharge in a magneticfield

Using the basic moment equations (number density, flow density, and energy density) for singly ionized argon and for electrons, a simple diffusion equation (essentially one proposed by Lieberman and Lichtenberg, 1994) is adopted (by comparison with experiment), together with an integrated power balance equation. The effects of scaling magnetic field and radius are then discussed first for simple cylinders, for which there are known analytic diffusion solutions. For specific cases having the more complicated geometry of two abutting coaxial cylinders with considerably different radii, the numerical results are well approximated and delimited by considering only the wider cylinder for low magnetic field, and at high magnetic field, where end effects dominate, using the total length and the smallest diameter of the system