Thienoisatin Oligomers as N-Type Molecular Semiconductors

Organic field effect transistors (OFETs) offer many advantages compared to traditional inorganic transistors, such as flexibility and solution processability. In this study we design and synthesize two thienoisatin-based organic semiconducting small molecules, then investigate their electronic properties in n-type OFETs. To introduce n-type charge transport, electron-withdrawing dicarbonitrile moieties were installed on thienoisoindigo and bis-thienoisatin molecules, which led to a quinoidal conjugation on thienoisoindigo, while maintaining an aromatic conjugation on the bis-thienoisatin. Following the syntheses, the molecules were characterized to determine highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels via cyclic voltammetry, as well as any potential radical properties

The proteins of the human erythrocyte plasma membrane with respect to in vivo ageing

Fresh human red blood cells were fractionated according to their in vivo age by simple centrifugation in order that changes in the membrane proteins could be investigated. Accepted criteria were used to assess the fractionation obtained, A packed column of the youngest cells was found to contain much more extra-cellular space when compared to the oldest cells and the evidence pointed to this having arisen from a difference in surface charge repulsion rather than geometry, 25% of both the youngest and oldest cells appeared to be sphered. Analysis of the membrane proteins by SDS PAGE revealed an increase in proteins 2.5 and 4.1 and a decrease in protein 7 with age. A tentative classification of the proteins revealed by SDS PAGE was put forward based on their age-dependent behaviour and in situ loci, special attention being paid to membrane-cytoplasm interactions . In vitro ageing was found to produce quantitatively very different changes in the membrane proteins. The large increase in protein 4.l with age and the temperature dependence of its binding to the membrane made its isolation seem worthwhile. A protein which was almost certainly 4.1 was purified from the cytoplasm of outdated blood. A method was developed for the total solubilisation of the membrane proteins, permitting polyacrylamide gel electrophoresis whilst maintaining a very high degree of functional integrity. This was achieved using the four nonionic surfactants NP40, B35, T20 and T40. LDH, PNP, AChEase, NADH-MR and GAPD were visualised with this system and of these PNP, AChEase and NADH-MR exhibited an age-dependent decrease in band intensity. LDH was resolved into four discrete isozyme bands and PNP appeared to contain many unresolved bands. Nine membrane-associated enzymes were assayed by standard techniques. No change was found for Na, K-ATPase and GAPD but the specific activities of AChEase, PGK, PNP, AKase, Mg-ATPase, NADH-MR and alkaline phosphatase were all found to decrease with age by varying amounts. Reticulocyte contamination could only have accounted for the small AChEase decrease. Of the rest, all the decreases were considered to be genuinely age-dependent, although only the decreases in NADH-MR and alkaline phosphatase could unequivocally be said to have given a good indication of the in situ situation. The other decreases could easily have been caused by a decrease in membrane integrity with age leading to a greater' loss of enzyme protein from the older membranes during ghost preparation

Conventional and Radiation Synthesis of Polymeric Nano- and Microgels and Their Possible Applications

Soft nanomaterials – polymeric nanogels and microgels – have made a fast and brilliant career, from an unwanted by-product of polymerization processes to an important and fashionable topic of interdisciplinary research in the fields of polymer chemistry and physics, materials science, pharmacy and medicine. Together with their larger analogues – macroscopic gels, most known in the form of water-swellable hydrogels – they have a broad field of actual and potential applications ranging from filler materials in coating industry to modern biomaterials.  A multitude of techniques has been described for the synthesis of polymeric nano- and microgels. Most of them can be classified in two groups. The first one are techniques based on concomitant polymerization and crosslinking (where the substrates are monomers or their mixtures), called by some authors "crosslinking polymerization". The second group are methods based on intramolecular crosslinking of macromolecules (where the starting material is not a monomer, but a polymer). The possibilities of employing macroscopic polymer gels as biomaterials, mostly in the form of hydrogels based on synthetic polymers, have been explored since 1960's, when these materials were first synthesized [1]. Since then, a number of products reached the stage of commercial application, soft contact lenses, drug delivery systems and wound dressings being the most widely known examples. Given the number of research groups involved and progress being made in this field, one may anticipate that in the future the number of hydrogel-based biomedical products on the market will be constantly increasing

Poly(vinyl methyl ether) hydrogels at temperatures below the freezing point of water - molecular interactions and states of water

Water interacting with a polymer reveals a number of properties very different to bulk water. These interactions lead to the redistribution of hydrogen bonds in water. It results in modification of thermodynamic properties of water and the molecular dynamics of water. That kind of water is particularly well observable at temperatures below the freezing point of water, when the bulk water crystallizes. In this work, we determine the amount of water bound to the polymer and of the so-called pre-melting water in poly(vinyl methyl ether) hydrogels with the use of Raman spectroscopy, dielectric spectroscopy, and calorimetry. This analysis allows us to compare various physical properties of the bulk and the premelting water. We also postulate the molecular mechanism responsible for the pre-melting of part of water in poly(vinyl methyl ether) hydrogels. We suggest that above −60 °C, the first segmental motions of the polymer chain are activated, which trigger the process of the pre-melting

Poly(vinyl methyl ether) hydrogels at temperatures below the freezing point of water - molecular interactions and states of water

Water interacting with a polymer reveals a number of properties very different to bulk water. These interactions lead to the redistribution of hydrogen bonds in water. It results in modification of thermodynamic properties of water and the molecular dynamics of water. That kind of water is particularly well observable at temperatures below the freezing point of water, when the bulk water crystallizes. In this work, we determine the amount of water bound to the polymer and of the so-called pre-melting water in poly(vinyl methyl ether) hydrogels with the use of Raman spectroscopy, dielectric spectroscopy, and calorimetry. This analysis allows us to compare various physical properties of the bulk and the premelting water. We also postulate the molecular mechanism responsible for the pre-melting of part of water in poly(vinyl methyl ether) hydrogels. We suggest that above −60 °C, the first segmental motions of the polymer chain are activated, which trigger the process of the pre-melting

Focal conduction block in the dorsal root ganglion in experimental allergic neuritis

Acute experimental allergic neuritis was induced in Lewis rats by inoculation with bovine intradural root myelin and adjuvants. In terminal experiments, sensory conduction was assessed in rats with hindlimb ataxia and weakness by stimulating the exposed sciatic nerve and recording directly from the exposed L-4 spinal nerve, dorsal root ganglion, dorsal root, and dorsal root entry zone. Focal conduction block was present in a high proportion of large-diameter fibers in the dorsal root ganglion. In contrast, nerve conduction in the peripheral nerve and spinal nerve was essentially normal apart from probable conduction block in some fibers in the proximal spinal nerve in a minority of rats. The afferent volley arriving at the dorsal root entry zone of the spinal cord was greatly reduced, as a consequence of the conduction block in the dorsal root ganglion and probable conduction block in the dorsal root. The M wave recorded from the fourth dorsal interosseus muscle of the hindfoot was normal in amplitude but slightly prolonged in latency and the H reflex was absent. These electrophysiological findings correlated well with the histological findings of inflammation and prominent demyelination in the dorsal root ganglia and dorsal roots with minimal involvement of the proximal spinal nerve and no involvement of the sciatic nerve. It is concluded that the hindlimb ataxia in rats with this form of acute experimental allergic neuritis is due to demyelination-induced nerve conduction block in the dorsal root ganglia and probably in the dorsal roots

Dielectric Properties and Characterisation of Titanium Dioxide Obtained by Different Chemistry Methods

We made comparison of titanium dioxide powders obtained from three syntheses including sol-gel and precipitation methods as well as using layered (tetramethyl)ammonium titanate as a source of TiO2. The obtained precursors were subjected to step annealing at elevated temperatures to transform into rutile form. The transformation was determined by Raman measurements in each case. The resulting products were characterised using Raman spectroscopy and dynamic light scattering. The main goal of the studies performed was to compare the temperature of the transformation in three titania precursors obtained by different methods of soft chemistry routes and to evaluate dielectric properties of rutile products by means of broadband dielectric spectroscopy. Different factors affecting the electrical properties of calcinated products were discussed. It was found that sol-gel synthesis provided rutile form after annealing at 850°C with the smallest particles size about 20 nm, the highest value of dielectric permittivity equal to 63.7, and loss tangent equal to 0.051 at MHz frequencies. The other powders transformed to rutile at higher temperature, that is, 900°C, exhibit lower value of dielectric permittivity and had a higher value of particles size. The correlation between the anatase-rutile transformation temperature and the size of annealed particles was proposed.This work was financially supported by the National Science Center (Poland) grant awarded by Decision no. DEC-2011/03/D/ST5/06074. The authors are grateful to Professor Adam Tracz from the Polish Academy of Science in Lodz for his help in performing SEM investigations

Guillain-Barré syndrome: a century of progress

In 1916, Guillain, Barré and Strohl reported on two cases of acute flaccid paralysis with high cerebrospinal fluid protein levels and normal cell counts — novel findings that identified the disease we now know as Guillain–Barré syndrome (GBS). 100 years on, we have made great progress with the clinical and pathological characterization of GBS. Early clinicopathological and animal studies indicated that GBS was an immune-mediated demyelinating disorder, and that severe GBS could result in secondary axonal injury; the current treatments of plasma exchange and intravenous immunoglobulin, which were developed in the 1980s, are based on this premise. Subsequent work has, however, shown that primary axonal injury can be the underlying disease. The association of Campylobacter jejuni strains has led to confirmation that anti-ganglioside antibodies are pathogenic and that axonal GBS involves an antibody and complement-mediated disruption of nodes of Ranvier, neuromuscular junctions and other neuronal and glial membranes. Now, ongoing clinical trials of the complement inhibitor eculizumab are the first targeted immunotherapy in GBS

Визначний учений у галузі вітчизняної гіроскопії (до 90-річчя з дня народження академіка НАН України В.М. Кошлякова)

Peripheral myelin protein 2 (Pmp2, P2 or Fabp8), a member of the fatty acid binding protein family, was originally described together with myelin basic protein (Mbp or P1) and myelin protein zero (Mpz or P0) as one of the most abundant myelin proteins in the peripheral nervous system (PNS). Although Pmp2 is predominantly expressed in myelinated Schwann cells, its role in glia is currently unknown. To study its function in PNS biology, we have generated a complete Pmp2 knockout mouse (Pmp2(-/-) ). Comprehensive characterization of Pmp2(-/-) mice revealed a temporary reduction in their motor nerve conduction velocity (MNCV). While this change was not accompanied by any defects in general myelin structure, we detected transitory alterations in the myelin lipid profile of Pmp2(-/-) mice. It was previously proposed that Pmp2 and Mbp have comparable functions in the PNS suggesting that the presence of Mbp can partially mask the Pmp2(-/-) phenotype. Indeed, we found that Mbp lacking Shi(-/-) mice, similar to Pmp2(-/-) animals, have preserved myelin structure and reduced MNCV, but this phenotype was not aggravated in Pmp2(-/-) /Shi(-/-) mutants indicating that Pmp2 and Mbp do not substitute each other's functions in the PNS. These data, together with our observation that Pmp2 binds and transports fatty acids to membranes, uncover a role for Pmp2 in lipid homeostasis of myelinating Schwann cells

Erythropoietin Ameliorates Rat Experimental Autoimmune Neuritis by Inducing Transforming Growth Factor-Beta in Macrophages

Erythropoietin (EPO) is a pleiotropic cytokine originally identified for its role in erythropoiesis. In addition, in various preclinical models EPO exhibited protective activity against tissue injury. There is an urgent need for potent treatments of autoimmune driven disorders of the peripheral nervous system (PNS), such as the Guillain-Barré syndrome (GBS), a disabling autoimmune disease associated with relevant morbidity and mortality. To test the therapeutic potential of EPO in experimental autoimmune neuritis (EAN) - an animal model of human GBS – immunological and clinical effects were investigated in a preventive and a therapeutic paradigm. Treatment with EPO reduced clinical disease severity and if given therapeutically also shortened the recovery phase of EAN. Clinical findings were mirrored by decreased inflammation within the peripheral nerve, and myelin was well maintained in treated animals. In contrast, EPO increased the number of macrophages especially in later stages of the experimental disease phase. Furthermore, the anti-inflammatory cytokine transforming growth factor (TGF)-beta was upregulated in the treated cohorts. In vitro experiments revealed less proliferation of T cells in the presence of EPO and TGF-beta was moderately induced, while the secretion of other cytokines was almost not altered by EPO. Our data suggest that EPO revealed its beneficial properties by the induction of beneficial macrophages and the modulation of the immune system towards anti-inflammatory responses in the PNS. Further studies are warranted to elaborate the clinical usefulness of EPO for treating immune-mediated neuropathies in affected patients