Reversible siRNA-polymer conjugates by RAFT polymerization

A straightforward synthetic method to prepare pyridyl disulfide end functionalized poly(PEG acrylate) by RAFT polymerization for efficient and reversible conjugation to siRNA is described.     

Designed amino acid ATRP initiators for the synthesis of biohybrid materials

A synthetic strategy to prepare peptide-polymer conjugates with precise sites of attachment is described. Amino acids modified with atom transfer radical polymerization (ATRP) initiators for the polymerization of styrenes and methacrylates were prepared. Fmoc-4-(1-chloroethyl)-phenylalanine (5) was synthesized in four steps from Fmoc-tyrosine. HATU-mediated amidation with glycine-OMe resulted in dipeptide (6). The initiator was effective for Cu(I)/bipyridine mediated bulk polymerization of styrene. Kinetic studies indicated a controlled polymerization, with high conversion (97%), and a polydispersity index (PDI) of 1.25. Fmoc-O-(2-bromoisobutyryl)-serine tert-butyl ester (10) was synthesized from Fmoc-Ser(OTrt)-OH in three steps. This initiator was employed in the ATRP of 2-hydroxyethyl methacrylate (HEMA), and kinetic studies indicated a controlled polymerization. Different monomer to initiator ratios resulted in poly(HEMA) of different molecular weights and narrow PDIs (1.14-1.25). Conversions were between 70 and 99%. HEMA modified with N-acetyl-D-glucosamine (GlcNAc) was also polymerized to 84% conversion and the resulting PDI was 1.19. The t-butyl ester protecting group of 10 was removed, and the resulting amino acid (11) was incorporated into VM(11)VVQTK by standard solid-phase peptide synthesis. Polymerization resulted in the glycopolymer-peptide conjugate in 93% conversion and a PDI of 1.14.     

MACBETHSort: a multiple criteria decision aid procedure for sorting strategic products

Efficient companies need to know which their strategic products are. For this purpose, the ABC classification based on the item’s value was developed and was used for a long time. Later, it was recognised that several other criteria need to be considered and multi-criteria ranking methods were applied. However, the classes have always been defined based only on a relative proportion. Therefore, the number of products in a class is independent of the actual importance of the products. In this paper, a new sorting procedure MACBETHSort is introduced, which is an evolution of the choice, ranking and rating technique MACBETH. The procedure has been validated in a real case study for assigning access and entrance solutions in ABC classes.     

Kinetic mechanism of acetyl-CoA synthase: steady-state synthesis at variable Co/Co2 pressures.

Steady-state initial rates of acetyl-CoA synthesis (upsilon/[E(tot)]) catalyzed by acetyl-CoA synthase from Clostridium thermoaceticum (ACS) were determined at various partial pressures of CO and CO2. When [CO] was varied from 0 to 100 microM in a balance of Ar, rates increased sharply from 0.3 to 100 min(-1). At [CO] > 100 microM, rates declined sharply and eventually stabilized at 10 min(-1) at 980 microM CO. Equivalent experiments carried out in CO2 revealed similar inhibitory behavior and residual activity under saturating [CO]. Plots of upsilon/[E(tot)] vs [CO2] at different fixed inhibitory [CO] revealed that Vmax/[E(tot)] (kcat) decreased with increasing [CO]. Plots of upsilon/[E(tot)] vs [CO2] at different fixed noninhibitory [CO] showed that Vmax/[E(tot)] was insensitive to changes in [CO]. Of eleven candidate mechanisms, the simplest one that fit the data best had the following key features: (a) either CO or CO2 (at a designated reductant level and pH) activate the enzyme (E' + CO right arrow over left arrow E, E' + CO2/2e-/2H+ right arrow over left arrow E); (b) CO and CO2 are both substrates that compete for the same enzyme form (E + CO right arrow over left arrow ECO, E + CO2/2e-/2H+ right arrow over left arrow ECO, and ECO --> E + P); (c) between 3 and 5 molecules of CO bind cooperatively to an enzyme form different from that to which CO2 and substrate CO bind (nCO + ECO right arrow over left arrow (CO)nECO), and this inhibits catalysis; and (d) the residual activity arises from either the (CO)nECO state or a heterogeneous form of the enzyme. Implications of these results, focusing on the roles of CO and CO2 in catalysis, are discussed.     

On the reconstruction of linear codes

For a linear code over GF(q) we consider two kinds of “subcodes” called residuals and punctures. When does the collection of residuals or punctures determine the isomorphism class of the code? We call such a code residually or puncture reconstructible. We investigate these notions of reconstruction and show that, for instance, selfdual binary codes are puncture and residually reconstructible. A result akin to the edge reconstruction of graphs with sufficiently many edges shows that a code whose dimension is small in relation to its length is puncture reconstructible. © 1998 John Wiley & Sons, Inc. J Combin Designs 6: 285–291, 1998     

Synthesis of Biotinylated Aldehyde Polymers for Biomolecule Conjugation

Biotinylated polymers with side‐chain aldehydes were prepared for use as multifunctional scaffolds. Two different biotin‐containing chain transfer agents (CTAs) and an aldehyde‐containing monomer, 6‐oxohexyl acrylate (6OHA), are synthesized. Poly(ethylene glycol) methyl ether acrylate (PEGA) and 6OHA are copolymerized by reversible addition‐fragmentation chain transfer (RAFT) polymerization in the presence of the biotinylated CTAs. The resulting polymers are analyzed by GPC and¹H NMR spectroscopy. The polymer end groups contained a disulfide bond, which could be readily reduced in solution to remove the biotin. Reactivity of the aldehyde side chains is demonstrated by oxime and hydrazone formation at the polymer side chains, and conjugate formation of fluorescently labeled polymers with streptavidin is investigated by gel electrophoresis.

     

Demonstration of a spatial filtering amplifier for high-order harmonics

We report what is to our knowledge the first demonstration of spatial filtering of a high-order harmonic beam into a soft-x-ray laser plasma amplifier at 32.8 nm. After amplification the seed energy is enhanced by a factor of 50, and the beam profile of the amplified beam exhibits an Airy-like shape due to the spatial filtering by the optical field ionized plasma. Moreover, the transverse coherence of the spatially filtered amplified beam is strongly enhanced, resulting in the generation of a peak coherent power of 0.9 x 10(5) to 1.8 x 10(5) W.