Microwave-assisted hydrogel synthesis: a new method for crosslinking polymers in aqueous solutions

It has been found that hydrogels may be formed by microwave irradiation of aqueous solutions containing appropriate combinations of polymers. This new method of hydrogel synthesis yields sterile hydrogels without the use of monomers, eliminating the need for the removal of unreacted species from the final product. Results for two particularly successful combinations, poly(vinyl alcohol) with either poly(acrylic acid) or poly(methylvinylether-alt-maleic anhydride), are presented. Irradiation using temperatures of 100–150 °C was found to yield hydrogels with large equilibrium swelling degrees of 500–1000 g g−1. Material leached from both types of hydrogel shows little cytotoxicity towards HT29 cells.

Self-assembly of telechelic tyrosine end-capped PEO and poly(alanine) polymers in aqueous solution

The self-assembly in aqueous solution of three novel telechelic conjugates comprising a central hydrophilic polymer and short (trimeric or pentameric) tyrosine end-caps has been investigated. Two of the conjugates have a central poly(oxyethylene) (polyethylene oxide, PEO) central block with different molar masses. The other conjugate has a central poly(l-alanine) (PAla) sequence in a purely amino-acid based conjugate. All three conjugates self-assemble into β-sheet based fibrillar structures, although the fibrillar morphology revealed by cryogenic-TEM is distinct for the three polymers—in particular the Tyr5-PEO6k-Tyr5 forms a population of short straight fibrils in contrast to the more diffuse fibril aggregates observed for Tyr5-PEO2k-Tyr5 and Tyr3-PAla-Tyr3. Hydrogel formation was not observed for these samples (in contrast to prior work on related systems) up to quite high concentrations, showing that it is possible to prepare solutions of peptide–polymer-peptide conjugates with hydrophobic end-caps without conformational constraints associated with hydrogelation. The Tyr5-PEO6k-Tyr5 shows significant PEO crystallization upon drying in contrast to the Tyr5-PEO2k-Tyr5 conjugate. Our findings point to the remarkable ability of short hydrophobic peptide end groups to modulate the self-assembly properties of polymers in solution in model peptide-capped “associative polymers”. Retention of fluidity at high conjugate concentration may be valuable in potential future applications of these conjugates as bioresponsive or biocompatible materials, for example exploiting the enzyme-responsiveness of the tyrosine end-groups

ADCK3, an ancestral kinase, is mutated in a form of recessive ataxia associated with coenzyme Q(10) deficiency

Muscle coenzyme Q(10) (CoQ(10) or ubiquinone) deficiency has been identified in more than 20 patients with presumed autosomal-recessive ataxia. However, mutations in genes required for CoQ(10) biosynthetic pathway have been identified only in patients with infantile-onset multisystemic diseases or isolated nephropathy. Our SNP-based genome-wide scan in a large consanguineous family revealed a locus for autosomal-recessive ataxia at chromosome 1q41. The causative mutation is a homozygous splice-site mutation in the aarF-domain-containing kinase 3 gene (ADCK3). Five additional mutations in ADCK3 were found in three patients with sporadic ataxia, including one known to have CoQ(10) deficiency in muscle. All of the patients have childhood-onset cerebellar ataxia with slow progression, and three of six have mildly elevated lactate levels. ADCK3 is a mitochondrial protein homologous to the yeast COQ8 and the bacterial UbiB proteins, which are required for CoQ biosynthesis. Three out of four patients tested showed a low endogenous pool of CoQ(10) in their fibroblasts or lymphoblasts, and two out of three patients showed impaired ubiquinone synthesis, strongly suggesting that ADCK3 is also involved in CoQ(10) biosynthesis. The deleterious nature of the three identified missense changes was confirmed by the introduction of them at the corresponding positions of the yeast COQ8 gene. Finally, a phylogenetic analysis shows that ADCK3 belongs to the family of atypical kinases, which includes phosphomositide and choline kinases, suggesting that ADCK3 plays an indirect regulatory role in ubiquinone biosynthesis possibly as part of a feedback loop that regulates ATP production.

Microbiological assay for cefoxitin sodium in dosage form

A microbiological assay applying the cylinder-plate method is described for determination of the activity of cefoxitin sodium in injectables. Using a strain of Staphylococcus epidermidis ATCC 12226 as the test organism, cefoxitin sodium was measured in concentrations ranging from 50.0 to 200.0 mu g/mL. The validation showed that the method was linear (r = 0.9998), precise (RSD 0.81%), and accurate. It was concluded that the microbiological assay is satisfactory for quantitation of cefoxitin sodium in injectables.

Spectroscopic and electrochemical characterization of polyaniline and a ruthenium complex, mer-[RuCl3(dppb)(py)], in the form of Langmuir-Blodgett films

Langmuir monolayers and Langmuir-Blodgett (LB) films have been produced from polyaniline and a biphosphinic ruthenium complex, referred to as Rupy. Strong, repulsive interaction between the two components led to a nonlinear change in area per molecule and surface potential with the concentration of Rupy in the mixed film. Molecular interaction was also denoted in the spectroscopic and electrochemical properties of the Y-type LB transferred films. The Raman spectra of mixed PANI-Rupy films indicated that the degree of oxidation of PANI increased linearly with the concentration of Ropy. With PANI being increasingly oxidized by presence of Rupy, the electroactivity of the mixed films decreased with the amount of Rupy, to become undetectable when the mixed LB film is 501 mol in Rupy. The presence of Rupy caused the electrical properties of the mixed LB films to be less sensitive to environmental changes. The electrical capacitance of a mixed film changed only by 15% when the sample was taken from vacuum to air, whereas the change was 215% for a pure PANI LB film.

Ideas of four-fermion operators in electromagnetic form factor calculations

Four-fermion operators have been used in the past to link the quark-exchange processes in the interaction of hadrons with the effective meson-exchange amplitudes. In this paper, we apply the similar idea of a Fierz rearrangement to the self-energy and electromagnetic processes and focus on the electromagnetic form factors of the nucleon and the electron. We explain the motivation of using four-fermion operators and discuss the advantage of this method in computing electromagnetic processes. © 2013 American Physical Society.

Gamma-ray dosimetric properties of conjugated polymers in solution

The effect of gamma radiation on poly{[2,5-bis(3-(N,N-diethylamino)-1-oxapropyl)-1,4-phenylene]-alt-1,4- phenylene} (PPP); poly{[2,5-bis(3-(N,N-diethylammonium bromide)-1-oxapropyl)-1,4-phenylene]-alt-1,4-phenylene} (PPP-Br); and the polymerized dye poly-1-ethyl-2-[3-(1-ethyl-1,3-dihydro-3,3-dimethyl-2H-indol-2-ylidene)-1-propenyl]- 3,3-dimethyl-3H-indolium perchlorate (Poly-CyC) has been investigated. The stability and response of poly [2-methoxy- 5-(2'- ethyl-hexyloxy)-p-phenylenevinylene] (MEH-PPV) in mixed solutions have also been explored. To this end, samples with concentrations ranging from 0.005 to 0.500 mg/mL were irradiated with a 60Co gamma-ray source at room temperature, using doses up to 1 kGy, and the response was analyzed by UV-Vis spectroscopy. The obtained results reinforce the previously proposed mechanism and suggest that the effect depends on specific structural characteristics of the main chain of the polymers. Moreover, the polymerized dyes display interesting dosimetric properties. Additionally, it has been noted that, contrary to what happens in other solvents, MEH-PPV is degraded in bromoform solution. Protective effects have also been observed for bromoform+toluene mixtures (1:1 vol/vol) and solutions containing molecular dyes. - See more at: http://www.eurekaselect.com/117251/article#sthash.gHFnYvJk.dpuf

The processing of polyelectrolyte-covered magnetite nanoparticles in the form of nanostructured thin films

Magnetic nanoparticles are promising for a variety of applications, such as biomedical devices, spin electronics, magnetic data storage media, to name a few. However, these goals may only be reached if stable and organized structures are fabricated. In this article, we report on a single-step synthetic route with the coprecipitation method, in which iron oxide magnetic nanoparticles (Fe3O4 NPs) were stabilized in aqueous media using the poly(diallyldimethylammonium chloride) (PDAC) polyelectrolyte. The Fe3O4 NPs had a diameter of ca. 5 nm, according to transmission electron microscopy (TEM) images, being arranged in an inverse spinel structure typical of magnetite. An investigation with infrared spectroscopy indicated that the mechanisms of stabilization in the polymer matrix were based on the interaction between quaternary amide groups from PDAC and the nanoparticle surface. The Fe3O4-PDAC NPs exhibited considerable magnetic susceptibility, with a monotonic increase in the magnetization with decreasing temperature. These Fe3O4-PDAC NPs were immobilized in layer-by-layer (LbL) films, being alternated with layers of poly(vinylsulfonic acid) (PVS). The LbL films were much rougher than typical films made with polyelectrolytes, and Fe3O4-PDAC NPs have been responsible for the high electrocatalytic activity toward H2O2 reduction, with an overpotential shift of 0.69 V. Overall, the stability, magnetic properties and film-forming ability indicate that the Fe3O4-PDAC NPs may be used for nanoelectronics and bioelectrochemical devices requiring reversible and magnetic redox materials.

Influence of chain stiffness on structure and dynamics of polymers in the melt

Die vorliegende Arbeit beschaeftigt sich mit der Untersuchung vonPolymeren mit intrinsischer Steifigkeit. Es werden vor allem lokale statische unddynamische Eigenschaften anhand zweier verschiedener Simulationsmodellebetrachtet: Ein generisches Polymermodell, bei dem nur dieSteifigkeit als ein das spezifische Polymer charakterisierenden Parametereingeht und ein atomistisches Modell fuer trans-Polyisopren. Mit Hilfe des ersten Modells koennen Statik und Dynamik wurmartiger Kettenbeobachtet werden. Das Blob-Konzept ist eine angemessene statischeBeschreibung. Lokale Orientierungen haengen schwach von derSteifigkeit ab. Das Reptationsmodell kann die beobachtete Dynamik fuer lange Kettennicht mehr angemessen beschreiben. Lange Ketten bewegen sich, als obsie in Roehren gezwaengt waeren; jedoch ist die Bewegung starkabhaengig von der Steifigkeit. Fuer Ketten dieser Art konntequalitativ das Verhalten reproduziert werden, das in NMR-Experimentenbeobachtet wird. Eine Verhakungslaenge laesst sich fuer solche Kettenkaum mehr definieren. Dynamische Strukturfunktionen und insbesonderedie direkte Visualisierung der Ketten verdeutlichen die effektiv aufeine Roehre beschraenkte Bewegung. Das atomistische Polyisoprenmodell wurde mit verschiedenen Experimenten,verglichen. In den Simulationen bei konnten qualitativ undsemiquantitativ experimentelle Ergebnisse reproduziert werden. Zuletzt wurden die Laengen- und Zeitskalen der beiden Modelleerfolgreich aufeinander abgebildet.

Lipid remodelling of glycosylphosphatidylinositol (GPI) glycoconjugates in procyclic-form trypanosomes: biosynthesis and processing of GPIs revisited

The African trypanosome, Trypanosoma brucei, has been used as a model to study the biosynthesis of GPI (glycosylphosphatidylinositol) anchors. In mammalian (bloodstream)-form parasites, diacyl-type GPI precursors are remodelled in their lipid moieties before attachment to variant surface glycoproteins. In contrast, the GPI precursors of insect (procyclic)-form parasites, consisting of lyso-(acyl)PI (inositol-acylated acyl-lyso-phosphatidylinositol) species, remain unaltered before protein attachment. By using a combination of metabolic labelling, cell-free assays and complementary MS analyses, we show in the present study that GPI-anchored glycoconjugates in T. congolense procyclic forms initially receive tri-acylated GPI precursors, which are subsequently de-acylated either at the glycerol backbone or on the inositol ring. Chemical and enzymatic treatments of [3H]myristate-labelled lipids in combination with ESI-MS/MS (electrospray ionization-tandem MS) and MALDI-QIT-TOF-MS3 (matrix-assisted laser-desorption ionization-quadrupole ion trap-time-of-flight MS) analyses indicate that the structure of the lipid moieties of steady-state GPI lipids from T. congolense procyclic forms consist of a mixture of lyso-(acyl)PI, diacyl-PI and diacyl-(acyl)PI species. Interestingly, some of these species are myristoylated at the sn-2 position. To our knowledge, this is the first demonstration of lipid remodelling at the level of protein- or polysaccharide-linked GPI anchors in procyclic-form trypanosomes.

Perturbation of phosphatidylethanolamine synthesis affects mitochondrial morphology and cell-cycle progression in procyclic-form Trypanosoma brucei

Phosphatidylethanolamine (PE) and phosphatidylcholine (PC) are the two major constituents of eukaryotic cell membranes. In the protist Trypanosoma brucei, PE and PC are synthesized exclusively via the Kennedy pathway. To determine which organelles or processes are most sensitive to a disruption of normal phospholipid levels, the cellular consequences of a decrease in the levels of PE or PC, respectively, were studied following RNAi knock-down of four enzymes of the Kennedy pathway. RNAi against ethanolamine-phosphate cytidylyltransferase (ET) disrupted mitochondrial morphology and ultrastructure. Electron microscopy revealed alterations of inner mitochondrial membrane morphology, defined by a loss of disk-like cristae. Despite the structural changes in the mitochondrion, the cells maintained oxidative phosphorylation. Our results indicate that the inner membrane morphology of T. brucei procyclic forms is highly sensitive to a decrease of PE levels, as a change in the ultrastructure of the mitochondrion is the earliest phenotype observed after RNAi knock-down of ET. Interference with phospholipid synthesis also impaired normal cell-cycle progression. ET RNAi led to an accumulation of multinucleate cells. In contrast, RNAi against choline-/ethanolamine phosphotransferase, which affected PC as well as PE levels, caused a cell division phenotype characterized by non-division of the nucleus and production of zoids.

Reduplication in Mapuzungun: form and function

Mapuzungun has reduplicative structures based on elements other than verb stems that are of very limited productivity. With verb stems, however, several formal patterns can be distinguished, which consist of the repetition of the lexical verb stem plus the addition of an apparently grammaticalized version of one of three verb roots or a zero morpheme. The previous literature has attempted to identify form/function correlations for these more or less productive verbal reduplicative patterns, and the present paper contributes to the discussion by surveying older studies and exploring several cases that suggest that such form/function correspondences are substantially less straightforward than a casual observer might think.