Poly(2-hydroxyethyl acrylate-co-ethyleneglycol dimethacrylate) monoliths synthesized by radiation polymerization in a mold

Copolymer monoliths of diethyleneglycol dimethacrylate and 2-hydroxyethyl-acrylate were prepared by using the advantage of radiation initiated polymerization over the thermally initiated polymerization, namely, that it is sufficient to use only a monomer and a porogenic solvent and no initiator is needed. Besides, the reaction can take place at any desired temperature in a mold of suitable size and shape.The results showed that increase of the HEA content in the comonomer mixture (up to 18 vol%) resulted in monoliths with increased pore size and hydrophilic character. The specific surface area of these monoliths was in the order of 1 m²/g. The porous properties could be fine-tuned by changing the solvent.Flow rate measurements for several eluents indicated that these monoliths could be useful as chromatographic columns. This is illustrated by separation of several amino acids.     

Combined exposure to cyanobacterial biomass, lead and the Newcastle virus enhances avian toxicity

Under environmental conditions, wild birds can be exposed to multiple stressors including natural toxins, anthropogenic pollutants and infectious agents at the same time.This experimental study was successful in testing the hypothesis that adverse effects of cyanotoxins, heavy metals and a non-pathogenic immunological challenge combine to enhance avian toxicity. Mortality occurred in combined exposures to naturally occurring cyanobacterial biomass and lead shots, lead shots and Newcastle vaccination as well as in single lead shot exposure. Mostly acute effects around day 10 were observed. On day 30 of exposure, there were no differences in the liver accumulation of lead in single and combined exposure groups. Interestingly, liver microcystin levels were elevated in birds co-exposed to cyanobacterial biomass together with lead or lead and the Newcastle virus. Significant differences in body weights between all Pb-exposed and Pb-non-exposed birds were found on days 10 and 20. Single exposure to cyanobacterial biomass resulted in hepatic vacuolar dystrophy, whereas co-exposure with lead led to more severe granular dystrophy. Haematological changes were associated with lead exposure, in particular. Biochemical analysis revealed a decrease in glucose and an increase in lactate dehydrogenase in single and combined cyanobacterial and lead exposures, which also showed a decreased antibody response to vaccination.The combined exposure of experimental birds to sub-lethal doses of individual stressors is ecologically realistic. It brings together new pieces of knowledge on avian health. In light of this study, investigators of wild bird die-offs should be circumspect when evaluating findings of low concentrations of contaminants that would not result in mortality on a separate basis. As such it has implications for wildlife biologists, veterinarians and conservationists of avian biodiversity.     

Structure and morphology of linear polyethylene extrudates induced by elongational flow

This study focuses on the structure, morphology, and properties of linear polyethylene (PE) profiles manufactured by continuous extrusion. High level of chain orientation was achieved using specific flow and processing conditions. An extrusion die with semihyperbolic convergency was used to generate high percentage of elongational flow and chain extension. Simultaneously, high extrusion pressure and relatively low melt temperature led to flow‐induced crystallization of PE extended chains. The structure of PE tapes consists of crystal aggregates with different level of orientation and crystallinity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Molded rigid polymer monoliths as separation media for capillary electrochromatography. 2. Effect of chromatographic conditions on the separation

Monolithic columns for capillary electrochromatography have been prepared within the confines of untreated fused-silica capillaries in a single step by a simple copolymerization of mixtures of butyl methacrylate, ethylene dimethacrylate, and 2-acrylamido-2-methyl-1-propane-sulfonic acid (AMPS) in the presence of a porogenic solvent. The use of these novel macroporous monoliths eliminates the need for frits, the difficulties encountered with packed capillaries, and capillary surface functionalization. Since the porous properties of the monolithic materials can be easily tailored through changes in the composition of the ternary porogenic solvent, the effects of both pore size and the percentage of sulfonic acid monomer on the efficiency and the electroosmotic flow velocity of the capillary columns could be studied independently over a broad range. A simple increase in the content of charged functionalities within the monolith leads to an expected acceleration of the flow velocity. However, increasing the pore size leads to a substantial deterioration of the efficiency of the separation. In contrast, monoliths with increasing levels of AMPS in which the pore size remains fixed due to adjustments in the composition of the porogenic solvent show no deterioration in efficiency while maintaining the same increase in flow velocity, thus producing a significant reduction in separation time. Additionally, measurements on monoliths with constant levels of AMPS but different pore sizes suggest that flow velocity may be affected by the flow resistance within the capillary column.     

Monodisperse polymer beads as packing material for high-performance liquid chromatography

A novel approach to monodispersed porous polymer beads allowing accurate control over a broad range of pore size distribution has been developed. It involves the use of monodispersed template particles which are used as polymeric porogens in the suspension polymerization of monomers such as styrene and divinylbenzene. The size uniformity of the template particles is retained by the final porous beads. The porous properties of the final beads are determined in large part by the characteristics of the porogenic mixture such as its composition, the molecular weight of the polymeric porogen, as well as the relative amount of monomers, polymeric and low molecular weight porogens used.     

Monodisperse hydrolyzed poly(glycidyl methacrylate-co-ethylene dimethacrylate) beads as a stationary phase for normal-phase HPLC

The basic characteristics of a rugged, stable, and highly efficient polymeric stationary phase for normal-phase HPLC prepared by hydrolysis of porous monodisperse poly(glycidyl methacrylate-co-ethylene dimethacrylate) beads have been studied and compared with those of bare Nucleosil silica and Nucleosil silica-diol. As a result of their overall chemical composition and the more than 10-fold larger surface coverage with hydroxyl groups, the polymer beads provide much higher retention of model solute molecules. In contrast to silica hydroxyls, all of the polymer surface diol groups are chemically equal and homogeneously distributed over all of the surface. In addition, they are less acidic than typical silanol functionalities. The exceptional selectivity of the polymeric column can be controlled by the composition of the mobile phase, as demonstrated with a broad spectrum of separations involving positional isomers of benzene derivatives, nonpolar isobutylene copolymers with minute composition differences, and hydrophilic poly(ethylene oxides) differing only in their chain length. Unlike silica phases, the properties of the polymeric stationary phrase are not affected by the presence of water in the mobile phase. As a result, repetitive gradient separations in eluents ranging in polarity from hexane through tetrahydrofuran to water can be easily accomplished.     

Fast ion-exchange HPLC of proteins using porous poly(glycidyl methacrylate-co-ethylene dimethacrylate) monoliths grafted with poly(2-acrylamido-2-methyl-1-propanesulfonic acid)

Porous poly(glycidyl methacrylate-co-ethylene dimethacrylate) monoliths with different porous properties grafted with poly(2-acrylamido-2-methyl-1-propanesulfonic acid) chains using cerium(IV) initiated free-radical polymerization have been prepared and used for the separation of proteins in ion-exchange HPLC mode. Because of the presence of the large pores that are typical of monolithic separation media which allow easy flow of all of the mobile phase, the efficiency of the columns does not deteriorate even at high flow velocities as a result of the specific morphology of the monoliths. Optimization of the chromatographic conditions such as the shape of the mobile phase gradient and the flow rate allows for very fast separation of three proteins in less than 1.5 min.     

Resistance pattern of 2816 isolates isolated from 17631 blood cultures and etiology of bacteremia and fungemia in a single cancer institution

A phase III, open label randomized study was conducted in 50 patients comparing halothane and sevoflurane for paediatric day case surgery. A graded inhalational induction resulted in only slightly more rapid induction with sevoflurane (3.34 +/- 0.92 versus 3.85 +/- 1.02 minutes; P > 0.05). In children receiving sevoflurane, systolic blood pressure decreased to a lesser extent during induction (143 +/- 19.2 versus 26.9 +/- 10.9 percent decrease from resting values; P < 0.01) and heart rate was maintained. Respiratory events (coughing, breath-holding, bronchospasm, laryngospasm) were more common during induction with halothane, and excitement more common in children receiving sevoflurane. Emergence times were significantly more rapid in children who had received sevoflurane (21.4 +/- 10.9 versus 33.1 +/- 13.7 minutes; P < 0.01). Objective pain/discomfort scores were higher in patients receiving sevoflurane at 10, 20, 30 and 40 minutes after arrival in the recovery room, and the incidence of excitement during emergence was higher in this group. It is concluded that sevoflurane is well tolerated for inhalational induction and has an improved cardiovascular profile compared to halothane. Emergence was significantly more rapid following sevoflurane.     

Chlorin-based supramolecular assemblies for artificial photosynthesis

Photosynthetic reaction center models consisting of zinc 9-desoxo-pyrochlorophyllide a primary electron donors, ZC, that are directly bonded at their 3-position to the 5-position of a 2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin ZP, which is in turn bonded at its 15-position to 2-triptycenenaphthoquinone, 2-triptycenebenzoquinone, 1-triptycenebenzoquinone, or N-(4-phenyl),N′-(n-octyl)-1,4,5,8-naphththalediimide 1, 2, 3, and 4, respectively, were prepared. Steric hindrance between adjacent substituents positions the π system of the chlorophyll perpendicular to that of the porphyrin. In turn, the π system of the chlorophyll is held about 60° to that of the O-O axis of the quinones in 1 and 2, parallel to the quinone O-O axis in 3, and parallel to the N-N axis in the diimide acceptor in 4. The resulting structures place the ZC donors in 1, 2, 3 and 4 at fixed center-to-center distances of 20, 18, 14, and 21 å from the acceptors, respectively. Photoexcitation of 1-4 in 2-methyltetrahydrofuran glass at 77K results in a single observable electron transfer reaction: ZC-ZP-X^1* ZC-ZP-X → ZC⁺-ZP-X⁻, where X = benzoquinone (BQ), naphthoquinone (No) or naphthalenediimide (NI), that occurs with τ = 4.5, 3.3, 2.0, and 2.0 ps for 1, 2, 3, and 4, respectively. The final ZC⁺-ZP-X⁻ radical pairs live for 12.7, 8.4, 2.5, and 10 ms at 77K in 1, 2, 3, and 4, respectively, and exhibit spin-polarized EPR spectra characteristic of spin-correlated radical pairs. The EPR spectra of 1-4 can be simulated using the distances and orientations of the radicals relative to one another determined from the molecular structures of 1-4. These long-lived, spin-polarized radical ion pairs closely mimic the bacteriochlorophyll cation - quinone anion radical pair produced in photosynthetic reaction centers and provide a useful tool for studying the interaction of the surrounding medium with the charge separated radical ion pair.