Electrochemical and bioelectrocatalytical properties of novel block-copolymers containing interacting ferrocenyl units

The electrochemical characterization of three different polystyrene-b-polybutadiene block copolymers functionalized with ferrocenyl units electronically communicated, PSm-PBn(HSiMeFc2)p where m=615, n=53, p=39 (1), m=375, n=92, p=76 (2) and m=455, n=204, p=170 (3), has been carried out both in solution and electrochemically deposited onto platinum electrodes. The bioelectrocatalytical properties of electrodes modified with the polymers in the nicotinamide dinucleotide (NADH) and glucose oxidase (GOx) oxidations have been investigated as a function of the constitution and structure of the polymers. The analytical properties of electrodes modified with these polymers as sensors of NADH and GOx are described. In addition, an amperometric biosensor for glucose, prepared by electrostatic immobilization of glucose oxidase onto a platinum electrode modified with one of the ferrocenyl block copolymers as an example, has been developed. The results confirm that electrodes modified with the examined copolymers act as efficient redox mediators for the electrocatalytic oxidation of both reduced nicotinamide dinucleotide cofactor and glucose oxidase. The reaction with NADH proceeds via formation of a charge-transfer intermediate before yielding the reaction products. This is a novel example of electrodes modified with ferrocene derivatives that can be applied to the determination of NADH without the use of diaphorase. The redox copolymers co-immobilized with glucose-oxidase have been successfully used as amperometric biosensors for glucose determinations. As expected these compounds allow using lower working potentials. The sensitivities and detection limits obtained are comparable or even better than those of other ferrocene-modified polymers mediator electrodes

Long-range correlations in non-equilibrium systems: Lattice gas automaton approach

In systems removed from equilibrium, intrinsic microscopic fluctuations become correlated over distances comparable to the characteristic macroscopic length over which the external constraint is exerted. In order to investigate this phenomenon, we construct a microscopic model with simple stochastic dynamics using lattice gas automaton rules that satisfy local detailed balance. Because of the simplicity of the automaton dynamics, analytical theory can be developed to describe the space and time evolution of the density fluctuations. The exact equations for the pair correlations are solved explicitly in the hydrodynamic limit. In this limit, we rigorously derive the results obtained phenomenologically by fluctuating hydrodynamics. In particular, the spatial algebraic decay of the equal-time fluctuation correlations predicted by this theory is found to be in excellent agreement with the results of our lattice gas automaton simulations for two different types of boundary conditions. Long-range correlations of the type described here appear generically in dynamical systems that exhibit large scale anisotropy and lack detailed balance.Comment: 23 pages, RevTeX; to appear in Phys. Rev.

Late activation of the 9-oxylipin pathway during arbuscular mycorrhiza formation in tomato and its regulation by jasmonate signalling

The establishment of an arbuscular mycorrhizal (AM) symbiotic interaction is a successful strategy for the promotion of substantial plant growth, development, and fitness. Numerous studies have supported the hypothesis that plant hormones play an important role in the establishment of functional AM symbiosis. Particular attention has been devoted to jasmonic acid (JA) and its derivates, which are believed to play a major role in AM symbiosis. Jasmonates belong to a diverse class of lipid metabolites known as oxylipins that include other biologically active molecules. Recent transcriptional analyses revealed up-regulation of the oxylipin pathway during AM symbiosis in mycorrhizal tomato roots and indicate a key regulatory role for oxylipins during AM symbiosis in tomato, particularly those derived from the action of 9-lipoxygenases (9-LOXs). Continuing with the tomato as a model, the spatial and temporal expression pattern of genes involved in the 9-LOX pathway during the different stages of AM formation in tomato was analysed. The effects of JA signalling pathway changes on AM fungal colonization were assessed and correlated with the modifications in the transcriptional profiles of 9-LOX genes. The up-regulation of the 9-LOX oxylipin pathway in mycorrhizal wild-type roots seems to depend on a particular degree of AM fungal colonization and is restricted to the colonized part of the roots, suggesting that these genes could play a role in controlling fungal spread in roots. In addition, the results suggest that this strategy of the plant to control AM fungi development within the roots is at least partly dependent on JA pathway activation

Automated radiofrequency-based US measurement of common carotid intima-media thickness in RA patients treated with synthetic vs synthetic and biologic DMARDs

Objective. To compare the carotid intima-media thickness (IMT) assessed with automated radiofrequency-based US in RA patients treated with synthetic vs synthetic and biologic DMARDs and controls. Methods. Ninety-four RA patients and 94 sex-and age-matched controls were prospectively recruited at seven centres. Cardiovascular (CV) risk factors and co-morbidities, RA characteristics and therapy were recorded. Common carotid artery (CCA)-IMT was assessed in RA patients and controls with automated radiofrequency-based US by the same investigator at each centre. Results. Forty-five (47.9%) RA patients had been treated with synthetic DMARDs and 49 (52.1%) with synthetic and biologic DMARDs. There were no significant differences between the RA patients and controls in demographics, CV co-morbidities and CV disease. There were significantly more smokers among RA patients treated with synthetic and biologic DMARDs (P = 0.036). Disease duration and duration of CS and synthetic DMARD therapy was significantly longer in RA patients treated with synthetic and biologic DMARDs (P<0.0005). The mean CCA-IMT was significantly greater in RA patients treated only with synthetic DMARDs than in controls [591.4 (98.6) vs 562.1 (85.8); P = 0.035] and in RA patients treated with synthetic and biologic DMARDs [591.4 (98.6) vs 558.8 (95.3); P = 0.040). There was no significant difference between the mean CCA-IMT in RA patients treated with synthetic and biologic DMARDs and controls (P = 0.997). Conclusion. Our results suggest that radiofrequency-based measurement of CCA-IMT can discriminate between RA patients treated with synthetic DMARDs vs RA patients treated with synthetic and biologic DMARDs

Shear-induced quench of long-range correlations in a liquid mixture

A static correlation function of concentration fluctuations in a (dilute) binary liquid mixture subjected to both a concentration gradient and uniform shear flow is investigated within the framework of fluctuating hydrodynamics. It is shown that a well-known $|\nabla c|^2/k^4$ long-range correlation at large wave numbers $k$ crosses over to a weaker divergent one for wave numbers satisfying $k<(\dot{\gamma}/D)^{1/2}$, while an asymptotic shear-controlled power-law dependence is confirmed at much smaller wave numbers given by $k\ll (\dot{\gamma}/\nu)^{1/2}$, where $c$, $\dot{\gamma}$, $D$ and $\nu$ are the mass concentration, the rate of the shear, the mass diffusivity and the kinematic viscosity of the mixture, respectively. The result will provide for the first time the possibility to observe the shear-induced suppression of a long-range correlation experimentally by using, for example, a low-angle light scattering technique.Comment: 8pages, 2figure

The immunomodulator PSK induces in vitro cytotoxic activity in tumour cell lines via arrest of cell cycle and induction of apoptosis

Background Protein-bound polysaccharide (PSK) is derived from the CM-101 strain of the fungus Coriolus versicolor and has shown anticancer activity in vitro and in in vivo experimental models and human cancers. Several randomized clinical trials have demonstrated that PSK has great potential in adjuvant cancer therapy, with positive results in the adjuvant treatment of gastric, esophageal, colorectal, breast and lung cancers. These studies have suggested the efficacy of PSK as an immunomodulator of biological responses. The precise molecular mechanisms responsible for its biological activity have yet to be fully elucidated.Methods The in vitro cytotoxic anti-tumour activity of PSK has been evaluated in various tumour cell lines derived from leukaemias, melanomas, fibrosarcomas and cervix, lung, pancreas and gastric cancers. Tumour cell proliferation in vitro was measured by BrdU incorporation and viable cell count. Effect of PSK on human peripheral blood lymphocyte (PBL) proliferation in vitro was also analyzed. Studies of cell cycle and apoptosis were performed in PSK-treated cells.Results PSK showed in vitro inhibition of tumour cell proliferation as measured by BrdU incorporation and viable cell count. The inhibition ranged from 22 to 84%. Inhibition mechanisms were identified as cell cycle arrest, with cell accumulation in G0/G1 phase and increase in apoptosis and caspase-3 expression. These results indicate that PSK has a direct cytotoxic activity in vitro, inhibiting tumour cell proliferation. In contrast, PSK shows a synergistic effect with IL-2 that increases PBL proliferation.Conclusion These results indicate that PSK has cytotoxic activity in vitro on tumour cell lines. This new cytotoxic activity of PSK on tumour cells is independent of its previously described immunomodulatory activity on NK cells.AGL was supported by FIS Postdoctoral Research Contract CP03/00111. Studies were partially supported by a grant from Kureha Chemical Industry (Japan)

Improved tools and strategies for the prevention and control of arboviral diseases: A research-to-policy forum

Background Research has been conducted on interventions to control dengue transmission and respond to outbreaks. A summary of the available evidence will help inform disease control policy decisions and research directions, both for dengue and, more broadly, for all Aedes-borne arboviral diseases. Method A research-to-policy forum was convened by TDR, the Special Programme for Research and Training in Tropical Diseases, with researchers and representatives from ministries of health, in order to review research findings and discuss their implications for policy and research. Results The participants reviewed findings of research supported by TDR and others. Surveillance and early outbreak warning. Systematic reviews and country studies identify the critical characteristics that an alert system should have to document trends reliably and trigger timely responses (i.e., early enough to prevent the epidemic spread of the virus) to dengue outbreaks. A range of variables that, according to the literature, either indicate risk of forthcoming dengue transmission or predict dengue outbreaks were tested and some of them could be successfully applied in an Early Warning and Response System (EWARS). Entomological surveillance and vector management. A summary of the published literature shows that controlling Aedes vectors requires complex interventions and points to the need for more rigorous, standardised study designs, with disease reduction as the primary outcome to be measured. House screening and targeted vector interventions are promising vector management approaches. Sampling vector populations, both for surveillance purposes and evaluation of control activities, is usually conducted in an unsystematic way, limiting the potentials of entomological surveillance for outbreak prediction. Combining outbreak alert and improved approaches of vector management will help to overcome the present uncertainties about major risk groups or areas where outbreak response should be initiated and where resources for vector management should be allocated during the interepidemic period. Conclusions The Forum concluded that the evidence collected can inform policy decisions, but also that important research gaps have yet to be filled