Incubation period in the 2,2,4,4‐tetramethyl‐1‐piperidinyloxy‐mediated thermal autopolymerization of styrene: Kinetics and simulations

Mechanisms and simulations of the induction period and the initial polymerization stages in the nitroxide‐mediated autopolymerization of styrene are discussed. At 120–125 °C and moderate 2,2,4,4‐tetramethyl‐1‐piperidinyloxy (TEMPO) concentrations (0.02–0.08 M), the main source of radicals is the hydrogen abstraction of the Mayo dimer by TEMPO [with the kinetic constant of hydrogen abstraction (k_h)]. At higher TEMPO concentrations ([N?] > 0.1 M), this reaction is still dominant, but radical generation by the direct attack against styrene by TEMPO, with kinetic constant of addition k_ad, also becomes relevant. From previous experimental data and simulations, initial estimates of k_h ≈ 1 and k_ad ≈ 6 × 10^?7 L mol^?1 s^?1 are obtained at 125 °C. From the induction period to the polymerization regime, there is an abrupt change in the dominant mechanism generating radicals because of the sudden decrease in the nitroxide radicals. Under induction‐period conditions, the simulations confirm the validity of the quasi‐steady‐state assumption (QSSA) for the Mayo dimer in this regime; however, after the induction period, the QSSA for the dimer is not valid, and this brings into question the scientific basis of the well‐known expression k_th[M]³ (where [M] is the monomer concentration and k_th is the kinetic constant of autoinitiation) for the autoinitiation rate in styrene polymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6962‐6979, 2006     

Computer-simulated diffraction patterns for metastable austenitic steels

The paper deals with the computer simulation of composite theoretical electron-diffraction patterns for metastable austenitic steels, containing deformation and martensite transformation structures. In many cases generated data can be used for interpretation of experimentally determined diffraction patterns. A few examples are presented which demonstrate that the application of the composite theoretical diffraction patterns may be complicated due to various diffraction effects which can modify the geometry of experimentally obtained diffraction patterns.     

Über die Reproduzierbarkeit der turbidimetrischen Bestimmung von Phosphorspuren mit Strychninmolybdostickstoff(V)säure

Microchimica Acta - Mit der turbidimetrischen Strychninnitrat-Methode für Phosphorspurenbestimmung nach der Version von Hegedüs und Dvorszky kann man nur dann ausgezeichnete...     

A novel phosphoramidite method for automated synthesis of oligonucleotides on glass supports for biosensor development

Two protocols for functionalization of glass supports with hexaethylene glycol (HEG)-linked oligonucleotides were developed. The first method (standard amidite protocol) made use of the 2-cyanoethyl-phosphoramidite derivative of 4,4′-dimethoxytrityl-protected HEG. This was first coupled to the support by standard solid-phase phosphoramidite chemistry followed by extension with a thymidylic acid icosanucleotide. Stepwise addition of the linker phosphoramidite graduated at 1% (relative to the total sites available) perstep at 50°C resulted in an optimal yield of immobilized oligonucleotides at a density of 2.24 × 10¹⁰ strands/mm². This observed loading maximum lies well below the theoretical maximum loading owing to nonspecific adsorption of HEG on the glass and subsequent blocking of reactive sites. Surface loadings as high as 3.73 × 10¹⁰/mm² and of excellent sequence quality were achieved with a reverse amidite protocol. The support was first modified into a 2-cyanoethyl-N,N-diisopropylphosphoramidite analog followed by coupling with 4,4′-dimethoxytrityl-protected HEG. This protocol is conveniently available when using a conventional DNA synthesizer. The reverse amidite protocol allowed for control of the surface loading at values suitable for subsequent analytical applications that make use of immobilized oligonucleotides as probes for selective hybridization of sample nucleic acids of unknown sequence and concentration.     

Squaric acid N-hydroxylamides: synthesis, structure, and properties of vinylogous hydroxamic acid analogues

The synthesis of squaric acid N-hydroxylamide esters 5 and amides 6 from dimethyl squarate 2a is described. These derivatives are analogues of the naturally occurring iron(III) chelator hydroxamic acid. On the basis of a comparative reactivity study, a concerted retro-Cope mechanism for the formation of the N-hydroxylamide esters 5 by reaction of dimethyl squarate with hydroxylamines is proposed. A preliminary iron(III) binding study of these hydroxamic acid analogues is presented, demonstrating binding of iron(III) to amides 6 in aqueous solutions, while the esters 5 did not show any sign of metal ion binding. 13C NMR spectroscopic data (chemical shift and spin-lattice relaxation time determination) of these and related derivatives delineate the resonance structures predominant in these molecules. The resonance structures of the derivatives rationalize their spectroscopic data, chemical reactivity, and iron(III) binding properties. Single-crystal X-ray structure analyses of squaric acid N-hydroxylamide ester 5b and squaric acid N-hydroxylamide amide 6c confirm their connectivity and provide structural evidence supporting the spectroscopically derived conclusions. The squaric acid N-hydroxylamides are potentially useful in the construction of chemosensors for iron(III).     

Precursor-directed biosynthesis of epothilone in Escherichia coli

Engineered biosynthetic pathways provide a powerful method for generating complex molecules. Precursor-directed biosynthesis, which combines chemical synthesis and enzymatic transformations, allows non-native starting materials to be incorporated into biosynthetic pathways. Using this approach, we achieved the production of the anticancer agent epothilone C in Escherichia coli. An E. coli strain was engineered to express the last three modules of the epothilone biosynthetic pathway (epoD-M6, epoE, and epoF) and the substrate required to complement the biosynthetic enzymes was obtained by chemical synthesis. Under high-density cell culture conditions, the E. coli strain processed exogenously fed synthetic substrate into epothilone C at levels comparable to the native host (1 mg/L) and at higher levels than other heterologous hosts. Importantly, this precursor-directed approach will allow chemical modifications to be introduced into the polyketide backbone and may ultimately provide access to epothilone analogues with improved pharmacological properties in quantities sufficient for clinical development.     

Assessing the biocompatibility of NiTi shape memory alloys used for medical applications

The present paper reviews aspects related to the biocompatibility of NiTi shape memory alloys used for medical applications. These smart metallic materials, which are characterised by outstanding mechanical properties, have been gaining increasing importance over the last two decades in many minimal invasive surgery and diagnostic applications, as well as for other uses, such as in orthodontic appliances. Due to the presence of high amounts of Ni, the cytotoxicity of such alloys is under scrutiny. In this review paper we analyse work published on the biocompatibility of NiTi alloys, considering aspects related to: (1) corrosion properties and the different methods used to test them, as well as specimen surface states; (2) biocompatibility tests in vitro and in vivo; (3) the release of Ni ions. It is shown that NiTi shape memory alloys are generally characterised by good corrosion properties, in most cases superior to those of conventional stainless steel or Co–Cr–Mo-based biomedical materials. The majority of biocompatibility studies suggest that these alloys have low cytotoxicity (both in vitro and in vivo) as well as low genotoxicity. The release of Ni ions depends on the surface state and the surface chemistry. Smooth surfaces with well-controlled structures and chemistries of the outermost protective TiO₂ layer lead to negligible release of Ni ions, with concentrations below the normal human daily intake.     

Solid-phase synthesis of phenols and pyridinones via arylboronation/oxidation protocol using aryl bromides

A sequence of two known reactions, palladium catalyzed arylboronation of arybromide and subsequent oxidation of arylboronate with oxone, has been carried out to prepare functionalized phenols and pyridin-2(1H)-one which were later loaded on to resin for solid-phase synthesis. Using these resin-bound templates, a number of solid-phase methods were developed to generate libraries of substituted phenols and pyridin-2(1H)-one.