Multistep electrochemical reduction path of clusters [Os3(CO)10(α-diimine)]: comparison of electrochemical and photochemical Os-Os(α-diimine) bond cleavage

Electrochemical reduction of the triangular clusters [Os-3(CO)(10)(alpha-dimine)] (alpha-dimine = 2,2'-bipyridine (bpy), 2,2'-bipyrimidine (bpym)) and [Os-3(CO)(10)(mu-bpym) ReBr(CO)(3)] produces primarily the corresponding radical anions. Their stability is strongly determined by the pi acceptor ability of the reducible alpha-dimine ligand, which decreases in the order mu-bpym > bpym >> bpy. Along this series, increasing delocalisation of the odd electron density in the radical anion over the Os(alpha-dimine) chelate ring causes weakening of the axial (CO)(4)Os-Os(CO)(2)(alpha-dimine) bond and its facile cleavage for alpha-diimine = bpy. In contrast, the cluster radical anion is inherently stable for the bridging bpym ligand, the strongest pi-acceptor in the studied series. In the absence of the partial delocalisation of the unpaired electron over the Re( bpym) chelate bond, the Os-3-core of the radical anion remains intact only at low temperatures. Subsequent one-electron reduction of [Os-3(CO)(10)(bpym)](center dot-) at T = 223 K gives the open-triosmium core (= Os-3*) dianion, [Os-3*(CO)(10)(bpym)](2-). Its oxidation leads to the recovery of parent [Os-3(CO)(10)( bpym)]. At room temperature, [Os-3*( CO)(10)(bpym)](2-) is formed along a two-electron (ECE) reduction path. The chemical step (C) results in the formation of an open- core radical anion that is directly reducible at the cathodic potential of the parent cluster in the second electrochemical (E) step. In weakly coordinating tetrahydrofuran, [Os-3*(CO)(10)( bpym)](2-) rapidly attacks yet non- reduced parent cluster molecules, producing the relatively stable open- core dimer [Os-3*(CO)(10)(bpym)](2)(2-) featuring two open- triangle cluster moieties connected with an ( bpym) Os - Os( bpym) bond. In butyronitrile, [Os-3*( CO)(10)(bpym)](2-) is stabilised by the solvent and the dimer [Os-3*(CO)(10)(bpym)](2)(2-) is then mainly formed by reoxidation of the dianion on reverse potential scan. The more reactive cluster [Os-3(CO)(10)(bpy)] follows the same reduction path, as supported by spectroelectrochemical results and additional valuable evidence obtained from cyclic voltammetric scans. The ultimate process in the reduction mechanism is fragmentation of the cluster core triggered by the reduction of the dimer [Os-3*(CO)(10)(alpha- diimine)](2)(2-). The products formed are [Os-2(CO)(8)](2-) and {Os(CO)(2)(alpha- diimine)}(2). The latter dinuclear fragments constitute a linear polymeric chain [Os( CO)(2)(alpha-dimine)] n that is further reducible at the alpha-dimine ligands. For alpha-dimine = bpy, the charged polymer is capable of reducing carbon dioxide. The electrochemical opening of the triosmium core in the [Os-3( CO)(10)(alpha-dimine)] clusters exhibits several common features with their photochemistry. The same Os-alpha-dimine bond dissociates in both cases but the intimate mechanisms are different.

Electro-optical properties of liquid crystal copolymers and their relationship to structural order

A range of side chain liquid crystal copolymers have been prepared using mesogenic and non-mesogenic units. It is found that high levels of the non-mesogenic moieties may be introduced without completely disrupting the organization of the liquid crystal phase. Incorporation of this comonomer causes a marked reduction in the glass transition temperature (Tg), presumably as a result of enhanced backbone mobility and a corresponding lowering of the nematic transition temperature, thereby restricting the temperature range for stability of the liquid crystal phase. The effect of the interactions between the various components of these side-chain polymers on their electro-optic responses is described. Infrared (i.r.) dichroism measurements have been made to determine the order parameters of the liquid crystalline side-chain polymers. By identifying a certain band (CN stretching) in the i.r. absorption spectrum, the order parameter of the mesogenic groups can be obtained. The temperature and composition dependence of the observed order parameter are related to the liquid crystal phase transitions and to the electro-optic response. It is found that the introduction of the non-mesogenic units into the polymer chain lowers the threshold voltage of the electro-optic response over and above that due to the reduction in the order parameter. The dynamic electro-optic responses are dominated by the temperature-dependent viscosity and evidence is presented for relaxation processes involving the polymer backbone which are on a time scale greater than that for the mesogenic side-chain units.

Ring-opening polymerization in molten PEEK: transient reduction of melt-viscosity by macrocyclic aromatic thioetherketones

Blends of PEEK with macrocyclic thioether-ketones show initial melt-viscosities reduced by more than an order of magnitude relative to the polymer itself, enabling more facile processing and fabrication. On raising the temperature of the melt, however, the macrocycle undergoes spontaneous, entropically-driven ring-opening polymerization (ED-ROP), so that the properties of the final polymer should not, in principle, be compromised by the presence of low-MW macrocyclic material.

Dimensionality reduction assisted tensor clustering

This paper is concerned with tensor clustering with the assistance of dimensionality reduction approaches. A class of formulation for tensor clustering is introduced based on tensor Tucker decomposition models. In this formulation, an extra tensor mode is formed by a collection of tensors of the same dimensions and then used to assist a Tucker decomposition in order to achieve data dimensionality reduction. We design two types of clustering models for the tensors: PCA Tensor Clustering model and Non-negative Tensor Clustering model, by utilizing different regularizations. The tensor clustering can thus be solved by the optimization method based on the alternative coordinate scheme. Interestingly, our experiments show that the proposed models yield comparable or even better performance compared to most recent clustering algorithms based on matrix factorization.

Secoiridoids delivered as olive leaf extract induce acute improvements in human vascular function and reduction of an inflammatory cytokine: a randomised, double-blind, placebo-controlled, cross-over trial

The leaves of the olive plant (Olea europaea) are rich in polyphenols, of which oleuropein and hydroxytyrosol (HT) are most characteristic. Such polyphenols have been demonstrated to favourably modify a variety of cardiovascular risk factors. The aim of the present intervention was to investigate the influence of olive leaf extract (OLE) on vascular function and inflammation in a postprandial setting and to link physiological outcomes with absorbed phenolics. A randomised, double-blind, placebo-controlled, cross-over, acute intervention trial was conducted with eighteen healthy volunteers (nine male, nine female), who consumed either OLE (51 mg oleuropein; 10mg HT), or a matched control (separated by a 4-week wash out) on a single occasion. Vascular function was measured by digital volume pulse (DVP), while blood collected at baseline, 1, 3 and 6 h was cultured for 24 h in the presence of lipopolysaccharide in order to investigate effects on cytokine production. Urine was analysed for phenolic metabolites by HPLC. DVP-stiffness index and ex vivo IL-8 production were significantly reduced (P < 0.05) after consumption of OLE compared to the control. These effects were accompanied by the excretion of several phenolic metabolites, namely HT and oleuropein derivatives, which peaked in urine after 8-24 h. The present study provides the first evidence that OLE positively modulates vascular function and IL-8 production in vivo, adding to growing evidence that olive phenolics could be beneficial for health.

Stimulation of Acidic Reduction of Nitrite to Nitric Oxide by Soybean Phenolics: Possible Relevance to Gastrointestinal Host Defense

This study aimed to evaluate the potential of soybean-promoted acidic nitrite reduction and to correlate this activity with the content of phenolics and with the bactericidal activity against Escherichia coli O157:H7. Extracts of embrionary axes and cotyledons enriched in phenolics increased (center dot)NO formation at acidic pH at values that were 7.1 and 4.5 times higher, respectively, when compared to the reduction of the nonenriched extracts. Among the various phenolics accumulated in the soybean extracts, five stimulated nitrite reduction in the following decreasing order of potency: epicatechin gallate, chlorogenic acid, caffeic acid, galic acid and p-coumaric acid. Extracts of embrionary axes presented higher contents of epicatechin gallate and caffeic acid, compared to that of cotyledons, indicating a positive correlation between activity of the extracts and content of phenolics with regard to nitrite reducing activity. Soybean extracts enriched in phenolics interacted synergistically with acidified nitrite to prevent E. coli O157:H7 growth. The results suggest that soybean phenolics may interfere with the metabolism of (center dot)NO in an acidic environment by accelerating the reduction of nitrite, with a potential antimicrobial effect in the stomach.

Development of a fast capillary electrophoresis method for the determination of propranolol-Total analysis time reduction strategies

The aim of this study was to develop a fast capillary electrophoresis method for the determination of propranolol in pharmaceutical preparations. In the method development the pH and constituents of the background electrolyte were selected using the effective mobility versus pH curves. Benzylamine was used as the internal standard. The background electrolyte was composed of 60 mmol L(-1) tris(hydroxymethyl)aminomethane and 30 mmol L(-1) 2-hydroxyisobutyric acid,at pH 8.1. Separation was conducted in a fused-silica capillary (32 cm total length and 8.5 cm effective length, 50 mu m I.D.) with a short-end injection configuration and direct UV detection at 214 nm. The run time was only 14 s. Three different strategies were studied in order to develop a fast CE method with low total analysis time for propranolol analysis: low flush time (Lflush) 35 runs/h, without flush (Wflush) 52 runs/h, and Invert (switched polarity) 45 runs/h. Since the three strategies developed are statistically equivalent, Mush was selected due to the higher analytical frequency in comparison with the other methods. A few figures of merit of the proposed method include: good linearity (R(2) > 0.9999); limit of detection of 0.5 mg L(-1): inter-day precision better than 1.03% (n = 9) and recovery in the range of 95.1-104.5%. (C) 2009 Elsevier B.V. All rights reserved.

Reduction of Models in the Presence of Nuisance Parameters

In many statistical inference problems, there is interest in estimation of only some elements of the parameter vector that defines the adopted model. In general, such elements are associated to measures of location and the additional terms, known as nuisance parameters, to control the dispersion and asymmetry of the underlying distributions. To estimate all the parameters of the model and to draw inferences only on the parameters of interest. Depending on the adopted model, this procedure can be both algebraically is common and computationally very costly and thus it is convenient to reduce it, so that it depends only on the parameters of interest. This article reviews estimation methods in the presence of nuisance parameters and consider some applications in models recently discussed in the literature.

A comparative assessment of austempered ductile iron as a substitute in weight reduction applications

Manufacturing engineering has had to undergo drastic changes in the approach to material selection in order to meet new design challenges. In the automotive industry, researchers in their effort to reduce emissions and satisfy environmental regulations, have shifted their focus to new emerging materials such as high-strength aluminium alloys, metal matrix composites, plastics, polymers and of late, Austempered Ductile Iron (ADI). ADI is a good choice for design where the criterion is high performance at reduced weight and cost. The unique, ausferrite microstructure gives the material desirable material properties and an edge over other materials. A comparative study of ADI in terms of materials properties and machining characteristics with other materials is desirable to highlight the potential of the material. This paper focuses on a comparative assessment of material and machining characteristics of ADI for different applications. The properties under consideration are machinability, weight and cost savings and versatility. ADI has a higher strength-to-weight ratio than aluminium making it a ready alternative for material selection. In terms of machinability, there are some problems associated with machining of ADI due to its work hardening nature. This paper attempts to identify the possible potential applications of ADI, by critically reviewing specific applications such as machinability, overall economics and service.

Powdered activated carbon for fouling reduction of membrane in a pilot-scale recirculation aquaculture system

Recirculating aquaculture systems (RAS) are essential for the reduction in fresh water usage as well as the discharge of nutrients along with aquaculture effluents. A RAS consisting of an anoxic reactor, a membrane bioreactor (MBR) and a UV-disinfection unit was used to process 10,000 L/d of aquaculture effluent providing high-quality treated water for recirculation to a Barramundi fish culture. The system maintained low levels of nitrate (<20 mg/L), nitrite (<3 mg/L) and ammonia (<0.6 mg/L) in the fish tank. Permeate from the membrane that was recirculated to the fish tank contained <21 mg/L of nitrate, <2 mg/L of nitrite and 0 mg/L of ammonia. However, the rate of fouling of the membrane in the MBR was around 1.47 kPa/d, and the membrane in the MBR required cleaning due to fouling after 16 days. Cleaning of the membrane was initiated when the TMP reached around 25 to 30 kPa. In order to reduce the rate of fouling, 500 mg of powdered activated carbon (PAC) per litre of MBR volume was introduced, which decreased the rate of fouling to 0.90 kPa/d. Cleaning of membrane was needed only after 31 days of operation while maintaining the treated effluent quality. Thus the frequency of cleaning could be halved due to the introduction of PAC into the MBR.

Feature reduction to speed up malware classification

In statistical classification work, one method of speeding up the process is to use only a small percentage of the total parameter set available. In this paper, we apply this technique both to the classification of malware and the identification of malware from a set combined with cleanware. In order to demonstrate the usefulness of our method, we use the same sets of malware and cleanware as in an earlier paper. Using the statistical technique Information Gain (IG), we reduce the set of features used in the experiment from 7,605 to just over 1,000. The best accuracy obtained in the former paper using 7,605 features is 97.3% for malware versus cleanware detection and 97.4% for malware family classification; on the reduced feature set, we obtain a (best) accuracy of 94.6% on the malware versus cleanware test and 94.5% on the malware classification test. An interesting feature of the new tests presented here is the reduction in false negative rates by a factor of about 1/3 when compared with the results of the earlier paper. In addition, the speed with which our tests run is reduced by a factor of approximately 3/5 from the times posted for the original paper. The small loss in accuracy and improved false negative rate along with significant improvement in speed indicate that feature reduction should be further pursued as a tool to prevent algorithms from becoming intractable due to too much data.

Oxygen reduction reaction activity of La-based perovskite oxides in alkaline medium : a thin-film rotating ring-disk electrode study

In this work, LaMO₃ and LaNi_0.5M_0.5O₃ (M = Ni, Co, Fe, Mn and Cr) perovskite oxide electrocatalysts were synthesized by a combined ethylenediaminetetraacetic acid-citrate complexation technique and subsequent calcinations at 1000 °C in air. Their powder X-ray diffraction patterns demonstrate the formation of a specific crystalline structure for each composition. The catalytic property of these materials toward the oxygen reduction reaction (ORR) was studied in alkaline potassium hydroxide solution using the rotating disk and rotating ring-disk electrode techniques. Carbon is considered to be a crucial additive component because its addition into perovskite oxide leads to optimized ORR current density. For LaMO₃ (M = Ni, Co, Fe, Mn and Cr)), in terms of the ORR current densities, the performance is enhanced in the order of LaCrO₃, LaFeO₃, LaNiO₃, LaMnO₃, and LaCoO3. For LaNi_0.5M_0.5O₃, the ORR current performance is enhanced in the order of LaNi_0.5Fe_0.5O₃, LaNi_0.5Co_0.5O₃, LaNi_0.5Cr_0.5O₃, and LaNi_0.5Mn_0.5O₃. Overall, LaCoO₃ demonstrates the best performance. Most notably, substituting half of the nickel with cobalt, iron, manganese, or chromium translates the ORR to a more positive onset potential, suggesting the beneficial catalytic effect of two transition metal cations with Mn as the most promising candidate. Koutecky–Levich analysis on the ORR current densities of all compositions indicates that the four-electron pathway is favored on these oxides, which are consistent with hydroperoxide ion formation of <2%.

The significant effect of the phase composition on the oxygen reduction reaction activity of a layered oxide cathode

Layered oxides of Sr4Fe4Co2O13 (SFC2) which contains alternating perovskite oxide octahedral and polyhedral oxide double layers are attractive for their mixed ionic and electronic conducting and oxygen reduction reaction properties. In this work, we used the EDTA–citrate synthesis technique to prepare SFC2 and vary the calcination temperature between 900 and 1100 _C to obtain SFC2, containing different phase content of perovskite (denoted as SFC-P) and (Fe,Co) layered oxide phases (SFC-L). Rietveld refinements show that the SFC-P phase content increased from _39 wt% to _50 wt% and _61 wt% as the calcination temperature increased from 900 _C (SFC2-900) to 1000 _C (SFC2-1000) and 1050 _C (SFC2-1050). At 1100 _C (SFC2-1100), SFC-P became the dominant phase. The oxygen transport properties (e.g. oxygen chemical diffusion coefficient and oxygen permeability), electrical conductivity and oxygen reduction reaction activity is enhanced in the order of SFC2-1000, SFC2-1100 and SFC2-1050. The trend established here therefore negates the hypothesis that the perovskite phase content correlates with the oxygen transport property enhancement. The results suggest instead that there is an optimum composition value (e.g. 61 wt% of SFC-L for SFC2-1050 in this work) on which synergistic effects take place between the SFC-P and SFC-L phase.

Effect of feed temperature and membrane orientation on pre-treatment sludge volume reduction through forward osmosis

This study focuses on volume reduction of pre-treatment sludge as well as on dilution of reverse osmosis (RO) concentrate through emerging forward osmosis (FO) technology where RO concentrate draws water from the pre-treatment sludge (feed solution) in order to reduce pre-treatment sludge volume and increase the RO water recovery. Experiments were carried out using two different types of sludge i.e. (1) synthetic pre-treatment sludge (Lab sludge) which has lower salinity and (2) actual sludge from Perth Seawater Desalination Plant, Australia (Perth Seawater Desalination Plant (PSDP) sludge) which has higher salinity. Effect of membrane orientation (FO and pressure-retarded osmosis (PRO) modes) and temperature of pre-treatment sludge on permeate water flux was investigated. There was a significant increase in water flux from 3.2 to 10.2 LMH (i.e. ~3 times higher) when temperature increased from 20 to 40°C for Lab sludge in PRO mode. However, there is no significant effect of temperature on water flux in FO mode for Lab sludge. On the contrary for PSPD sludge, there was no effect on water flux with increase in temperature at PRO mode. Dissolved ions in the porous side increased the severity of concentrative internal concentration polarization; hence, it could reduce the flux. There was no significant change in water flux when temperature increased from 20 to 40°C for PSDP sludge in FO mode. However, higher amount of water has permeated from Lab sludge compared to PSDP sludge in FO mode. © 2014 © 2014 Balaban Desalination Publications. All rights reserved.

Reduction capability of soil humic substances from the Rio Negro basin, Brazil, towards Hg(II) studied by a multimethod approach and principal component analysis (PCA)

This paper characterizes humic substances (HS) extracted from soil samples collected in the Rio Negro basin in the state of Amazonas, Brazil, particularly investigating their reduction capabilities towards Hg(II) in order to elucidate potential mercury cycling/volatilization in this environment. For this reason, a multimethod approach was used, consisting of both instrumental methods (elemental analysis, EPR, solid-state NMR, FIA combined with cold-vapor AAS of Hg(0)) and statistical methods such as principal component analysis (PCA) and a central composite factorial planning method. The HS under study were divided into groups, complexing and reducing ones, owing to different distribution of their functionalities. The main functionalities (cor)related with reduction of Hg(II) were phenolic, carboxylic and amide groups, while the groups related with complexation of Hg(II) were ethers, hydroxyls, aldehydes and ketones. The HS extracted from floodable regions of the Rio Negro basin presented a greater capacity to retain (to complex, to adsorb physically and/or chemically) Hg(II), while nonfloodable regions showed a greater capacity to reduce Hg(II), indicating that HS extracted from different types of regions contribute in different ways to the biogeochemical mercury cycle in the basin of the mid-Rio Negro, AM, Brazil. (c) 2007 Published by Elsevier B.V.