Plasticity and dystonia: a hypothesis shrouded in variability.

Studying plasticity mechanisms with Professor John Rothwell was a shared highlight of our careers. In this article, we discuss non-invasive brain stimulation techniques which aim to induce and quantify plasticity, the mechanisms and nature of their inherent variability and use such observations to review the idea that excessive and abnormal plasticity is a pathophysiological substrate of dystonia. We have tried to define the tone of our review by a couple of Professor John Rothwell's many inspiring characteristics; his endless curiosity to refine knowledge and disease models by scientific exploration and his wise yet humble readiness to revise scientific doctrines when the evidence is supportive. We conclude that high variability of response to non-invasive brain stimulation plasticity protocols significantly clouds the interpretation of historical findings in dystonia research. There is an opportunity to wipe the slate clean of assumptions and armed with an informative literature in health, re-evaluate whether excessive plasticity has a causal role in the pathophysiology of dystonia

Surfactant Aided Reductive Carbonylation of Nitrobenzene inWater Catalyzed by Pd Complexes

The catalytic carbonylation of nitroarenes is a field of high interest from a technological point of view, since provides an environmentally benign route to a number of important industrial products, such as isocyanates, carbamates, ureas, azoarenes and azoxyarenes, amines, amides, oximes and several types of heterocyclic compounds. The reductive carbonylation of nitrobenzene in water carried out by using Pd(II)-solvable catalyst precursors, leads to aniline, as major product. In the present paper we propose the micellar catalytic reductive carbonylation of nitrobenzene in water. The Pd(II) catalyst precursors tested are synthesized by using cheaper commercial insolvable ligands, such as triphenylphosphine (PPh3), 1,3- bis(diphenylphosphino)propane (dppp) and 1, 10-phenantroline (phen). The influence on the conversion and on the selectivity of such precursors has been evaluated in combination with commercial anionic (SDS), cationic (TBAB) and non ionic (Triton X 100) surfactants. We have found that all the Pd(II) complexes tested are efficiently dissolved in each O/W emulsions but the conversion is strongly influenced by the nature of ligand. By using Pd(OAc)2(PPh3)2, high selectivity towards azo- and azo-oxybenzene has been obtained. The influence of some reaction parameters has been further evaluated and optimized

Cathode Active Material Recycling from Spent Lithium Batteries: A Green (Circular) Approach Based on Deep Eutectic Solvents

The transition to a circular economy vision must handle the increasing request of metals required to satisfy the battery industry; this can be obtained by recycling and feeding back secondary raw materials recovered through proper waste management. Here, a novel and green proof-of-concept was developed, based on deep eutectic solvents (DESs) to fully and easily recover valuable metals from various cathode active materials, including LiMn2O4, LiNi0.5Mn1.5O4, and LiNi0.8Co0.2O2. DES composed of choline chloride and lactic acid could leach Li, Mn, Co, and Ni, achieving efficiency of 100 % under much milder conditions with respect to the previous literature. For the first time, to our best knowledge, a two-step approach was reported in the case of LiNi0.8Co0.2O2 for selective recovery of Li, Co, and Ni with high yield and purity. Furthermore, other cathode components, namely aluminum current collector and binder, were found to be not dissolved by the proposed DES, thus making a simple separation from the active material possible. Finally, this strategy was designed to easily regenerate and reuse the leaching solvents for more than one extraction, thus further boosting process sustainability

New insights into cortico-basal-cerebellar connectome: clinical and physiological considerations

The current model of the basal ganglia system based on the 'direct', 'indirect' and 'hyperdirect' pathways provides striking predictions about basal ganglia function that have been used to develop deep brain stimulation approaches for Parkinson's disease and dystonia. The aim of this review is to challenge this scheme in light of new tract tracing information that has recently become available from the human brain using MRI-based tractography, thus providing a novel perspective on the basal ganglia system. We also explore the implications of additional direct pathways running from cortex to basal ganglia and between basal ganglia and cerebellum in the pathophysiology of movement disorders

Pd(II)-catalyzed emulsion copolymerization of carbon monoxide with ethene in CH2Cl2/water as a solvent

Chemical, physical and mechanical characteristics of alt poly(1-oxo-trimethylene) [1] well fit with a wide range of industrial applications and recently several researchers have shown a renovated keen interest for the application of such a polymer in the field of fibers [2]. In order to obtain fibers, however, high molecular weight polymers are required. In some papers we have reported that high molecular weight polymers require high pressure and low temperature but the nature of the solvent must be considered too [2-4]. The choose of the solvent influences both the activity of the catalyst and the average molecular weight of the polymer. Usually the catalysis is efficiently carried out in methanol by using the [Pd(OAc)2(DPPP)] complex in the presence of an acid (p-toluenesulfonic, TsOH) [5] which leads to polymers with not so high average molecular weight. By replacing methanol with CH3COOH-water also [PdCl2(DPPP)] complex efficiently catalyzes the reaction leading also to an increase of the polymer molecular weight [3]. By continuing the research on the influence of the solvent on the molecular weight, here we report our preliminary results on the preparation of alt- poly(1-oxo-trimethylene) by emulsion catalytic polymerization. The [PdCl2(DPPP)] complex has been dissolved in a CH2Cl2-H2O emulsion and the productivity has been optimized

The catalytic copolymerization of ethene with carbon monoxide efficiently carried out in water/dichloromethane/sodium dodecylsulfate emulsion

The CO-ethene copolymerization has been efficiently carried out in the water/CH2Cl2 emulsion by using water insolvable Pd(II) complexes. By using the surfactant SDS very high molecular weight copolymers have been obtained with high productivity (ca. 13,000 g/(gPd.h))

An investigation of hydro-geochemical processes in coupled thermal, hydraulic, chemical and mechanical behaviours of unsaturated soils

The new model ahs then been applied to investigate relevant hydraulic and hydrogeochemical processes in a swelling clay.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Hydrogenation of nitrobenzene to 4-aminophenol in a fully reusable solvent system, by using Pt, Rh, Pd supported on carbon-CF3COOH catalytic system

4-Aminophenol is an important raw material for several products in the field of dyes, photographs and pharmaceutics. For instance, paracetamol (N-acetyl-4-aminophenol) a widely employed analgesic and antipyretic whose production is in continuous growth specially in the far east region. Industrial synthesis of paracetamol is based mainly on 4-aminophenol, which is obtained by three different routes: i) nucleophilic substitution of the Cl of the 4-chloronitrobenzene, ii) reduction of 4-nitro-phenol, iii) selective hydrogenation of nitrobenzene [1]. The selective hydrogenation of nitrobenzene is however, the most convenient from both economical and environmental point of view [1, 2]. The major concern of this process is, however, the presence of H2SO4, which is origin of corrosion, safety, environmental and separation problems. The reaction is typically carried out in CSTR in which the biphasic reaction medium is used to accomplish simultaneously the Pt catalyzed hydrogenation of nitrobenzene and the acid catalyzed Bamberger rearrangement of the intermediate N-phenylhydroxylamine. From environmental point of view, the major drawback of the process is the neutralization of the acidic phase, with the consequent by-production of sulfate salts, which are undesired wastes. Starting from recent results obtained in the Beckmann rearrangement of the cyclohexanone oxime in CH3CN-CF3COOH system [3], here we show some findings on the hydrogenation of nitrobenzene to 4-aminophenol in a single liquid phase CH3CN-H2O-CF3COOH and in the presence a hydrogenation catalyst. The easy of recovery of solvent and catalysts allows to develop a greener process than that based on the biphasic H2SO4-nitrobenzene syste

Cognitive processess and cognitive reserve in multiple sclerosis

Multiple Sclerosis (MS) is characterized by motor, cognitive, and neuropsychiatric symptoms, which can occur independently. While MS is traditionally considered an inflammatory disease of the white matter, degeneration of gray matter is increasingly recognized as an important contributor to the progressive cognitive decline. A protective factor against the progression of cognitive dysfunction in MS could be the cognitive reserve, defined as resistance to brain dysfunction. Aim of the present study is to evaluate the role of cognitive reserve for different aspects of cognitive dysfunction of patients with MS. We found that patients with MS and lower cognitive reserve have poorer neuropsychological performance and slower information speed processing. These findings support the notion that intellectual reserve may protect some aspects of cognitive function in patients with MS

Environmentally friendly corrosion inhibitor of the copper in 0.5 M sulphuric acid solution.

Environmentally friendly corrosion inhibitor of the copper in 0.5 M sulphuric acid solution. G. Quartarone,a L. Ronchin,a A. Vavasori,a C. Tortato,a L. Bonaldo.b aUniversity of Venice, Dep. of Chemistry, Dorsoduro. 2137, 30123 Venice. E-mail: [email protected] bLubrikn, production of additives for lubricant, via Dell’Artigianato, 38, 30030 Vicenza. Copper corrosion inhibition by gramine [3-(dimethylaminomethyl)indole] in the 0.5 M sulphuric acid solutions was studied in the temperature range 25-55 °C using electrochemical impedance spectroscopy techniques (EIS). Gramine was dissolved at various concentrations (from 5∙10-4 to 7.5∙10-3) in 0.5 M sulphuric acid. The surface preparation of the specimens was carried out using silicon carbide paper up to grade 1200. EIS measurements were performed after dipping the working electrode into the 0.5 M sulphuric acid solutions with or without inhibitor at Ecorr with an a.c. voltage amplitude of 5mV. The frequency range was swept between 100 kHz and 10 mHz with 10 point for hertz decade. The presence of gramine led to changes of the impedance plots in both shape and size. The plots of Nyquist exhibited that some impedance spectra consisted of one capacitive loop at the higher frequencies which was attributed to a faradaic process involving a charge transfer resistance in parallel with double-layer capacitance element [1]. The size of the capacitive arc increased by increasing the concentration of gramine. This indicated that gramine increased the charge transfer resistance and then it had an inhibiting effect on copper corrosion in 0.5 M sulphuric acid solutions. Inhibition efficiencies results showed that the gramine inhibited the copper corrosion in the temperature range 25-55 °C reaching the maximum value of 86% at 55 °C. Impedance spectra also showed a depression of Nyquist-plot semicircles that can be related to the surface heterogeneity due the microscopic roughness of the electrode surface and inhibitor adsorption [2]. Moreover at the lower frequencies in both the uninhibited solutions and inhibited ones by lower inhibitor concentrations, the Warburg impedance appeared. In the copper corrosion in oxygenated sulphuric acid solutions at Ecorr the anodic reaction is copper dissolution and cathodic reaction is oxygen reduction being the hydrogen discharge current density negligible as compared to oxygen reduction current density. Then the Warburg impedance could be attributed to oxygen transport from the bulk solution to the copper surface [3]. The adsorption behaviour of gramine followed Temkin’s isotherm. The values of the standard free energy of adsorption of the gramine at 25 °C, 35 °C, 45 °C and 55°C were calculed. A structural model of the interface copper/0.5 M H2SO4 was proposed. [1] O.E. Barcia and O.R. Mattos, Electrochim. Acta 35, 1990, 1601. [2] H. Ashassi-Sorkhabi, N. Ghalebsaz-Jeddi, F. Hasemzadeh and H. Jahani, Electrochim. Acta 51, 2006, 3848. [3] H. Ma, S. Chen, B. Yin, S. Zhao, X. Liu, Corros. Sci., 45, 2003, 867