The role of solvent on the doping of polyaniline with Fe(III) ions

The products formed from the reaction of emeraldine base polyaniline (EB-PANI) with Fe(III) ions in N-methyl-pyrrolidone (NMP), dimethylacetamide (DMA), dimethylformamide (DMF) and m-cresol media have been investigated using UV-VIS-NIR and resonance Raman (lambda(0) = 632.8 and 1064 nm) spectroscopies. Through these results it was verified that the different PANI forms in solution can be formed by the suitable choice of the solvent. The behavior of Fe(III)/EB-PANI in different solvents was rationalized in terms of the interactions among Fe(III) ions, EB-PANI and solvent. In basic NMP, DMA and DMF media, the reaction of Fe(III) with EB-PANI yields EB-PANI doping giving ES-PANI and/or the EB-PANI oxidation to PB-PANI. The formation of ES-PANI is favored in DMF while PB-PANI is formed in a greater extension in NMP and DMA. In acidic m-cresol, only ES-PANI is produced in Fe(III)/EB-PANI solutions indicating the important role played by the solvent in the nature of the product. (C) 2010 Elsevier B.V. All rights reserved.

Functionalization of PAMAM dendrimers with [Ru-III(edta)(H2O)](-)

The anchoring of K[Ru-III(edta)(Cl)] on poly(amidoamine) dendrimers (PAMAM of three generations G(x)/Ru (x = 0, 2 and 3)) through a peptide type bond yielded the aquo species, [Ru-III(edta)(H2O)] on dendrimer surface, and upon NO exposure, yielded their nitrosyl analogues, Gx/RuNO. Characterization of these compounds by elemental analysis, and a UV-vis, IR and C-13 NMR spectroscopies indicated the immobilization of 4,12 and 29 molecules of [Ru-III(edta)(H2O)](-) or of the nitrosyl complex [Ru(II)edta)NO] on the dendrimer surface for G(X) = 0, 2 and 3, respectively. For each complex the electrochemical spectrum presented only one redox process with redox potential values of -0.20 and -0.32 V(vs SCE) attributed to the Ru/Run and NO+/NO0 couples in G(x)/Ru and G./RuNO, respectively. The one-electron reduction of Gx/RuNO` generates Gx/RuNOo, which undergoes aquation with a k(-NO) of 2.1 +/- 0.7 x 10(-3) s(-1) (pH 1.0, mu = 0.2 mol/L, CF3COOH/NaCF3COO, 25 degrees C). The Gx/RuNO species induced a relaxing effect in aortic rings denuded of endothelium and exhibited in vitro assay trypanocidal activity. (c) 2008 Elsevier Inc. All rights reserved.

Determination of sodium oxalate in Bayer liquor using flow-analysis incorporating an anion exchange column and tris(2,2`-bipyridyl)ruthenium(II) chemiluminescence detection

Semi-automated flow injection instrumentation, incorporating a small anion exchange column coupled with tris(2,2′-bipyridyl)ruthenium(II) (Ru(bipy)₃²⁺) chemiluminescence detection, was configured and utilised to develop rapid methodology for the determination of sodium oxalate in Bayer liquors. The elimination of both negative and positive interferences from aluminium(III) and, as yet, unknown concomitant organic species, respectively are discussed. The robustness of the methodology was considerably enhanced by using the temporally stable form of the chemiluminescence reagent, tris(2,2′-bipyridyl)ruthenium(III) perchlorate in dry acetonitrile. Real Bayer process samples were analysed and the results obtained compared well with those performed using standard methods within industrial laboratories.

Detection of pyrrolizidine alkaloids using flow analysis with both acidic potassium permanganate and tris(2,2’-bipyridyl)ruthenium(II) chemiluminescence

For the first time, analytically useful chemiluminescence was elicited from the reactions of the pyrrolizidine alkaloids. Heliotrine, retronecine, supinine, monocrotaline and echinatine N-oxide yielded chemiluminescence upon reaction with tris(2,2′-bipyridyl)ruthenium(II) whilst lasiocarpine, its N-oxide and supinine elicited light upon reaction with acidic potassium permanganate. Detection limits for heliotrine were 1.25 × 10⁻⁷ M and 9 × 10⁻⁹ M for tris(2,2′-bipyridyl)ruthenium(III) perchlorate with flow injection analysis (FIA) and the silica-immobilised reagent (4-[4-(dichloromethylsilanyl)-butyl]-4′-methyl-2,2′-bipyridine)bis(2,2′-bipyridyl)ruthenium(II) with sequential injection analysis (SIA), respectively. Lasiocarpine was detectable at 1.4 × 10⁻⁷ M using acidic potassium permanganate with FIA. Additionally, the silica-immobilised reagent was optimised with respect to the oxidant (ammonium ceric nitrate) concentration and the aspiration times which afforded a detection limit for codeine of 5 × 10⁻¹⁰ M using SIA.

Tris(2,2´-bipyridyl)ruthenium(II) chemiluminescence

This paper critically reviews analytical applications of the chemiluminescence from tris(2,2-bipyridyl)ruthenium(II) and related compounds published in the open literature between mid-1998 and October 2005. Following the introduction, which summarises the reaction chemistry and reagent generation, the review divides into three major sections that focus on: (i) the techniques that utilise this type of detection chemistry, (ii) the range of analytes that can be determined, and (iii) analogues and derivatives of tris(2,2-bipyridyl)ruthenium(II).

Effect of oxidant type on the chemiluminescence intensity from the reaction of tris(2,2’-biyridyl)ruthenium(III) with various organic acids

An investigation into the chemiluminescence of fourteen organic acids and tris(2,2′-bipyridyl)ruthenium(II) was undertaken. Particular emphasis was placed upon the method of production of the reagent, tris(2,2′-bipyridyl)ruthenium(III), with cerium(IV) sulfate, potassium permanganate, lead dioxide and electrochemical generation. Analytically useful chemiluminescence was observed when Ce(IV) or potassium permanganate were employed as oxidants. The kinetics of analyte oxidation was related to the intensity of the chemiluminescence emission, which increased by three orders of magnitude for tartaric acid after 40 h of oxidation.

Investigation of Iron (III) desferrioxamine B oxalate ligand exchange by UV-vis spectroscopy: the next step in developing a quantitative analytical method for measuring bioavailable iron in marine ecosystems

To date there are no analytical techniques designed to exclusively measure bioavailable iron in marine environments. The goal of this research is to develop such a technique by isolating the bioavailable iron using the terrestrial siderophore desferrioxamine B (DFB). This project contained many challenging aspects, but the specific goal of this study was to develop a robust analytical technique for quantification of Fe(III)-DFB complexes at nanomolar concentrations. Past work showed that oxalate (Ox) promotes photodissociation of Fe(III)-DFB to Fe(Il), and we are specifically interested in the mechanism of this process. A model was developed using known thermodynamic constants for Fe(III)-DFB and Fe(III) oxalato complexes and adjusting for ionic strength. The model was confirmed by monitoring the UV-VIS absorbance of the system at a variety of oxalate concentrations and pH. The model did not include ternary complexes. Next., the rate of Fe(1I) production during UV irradiation was examined. The results showed that the rate of Fe(II) production was based entirely on the [Fe(Ox)?]3- speciation, and that reoxidation of Fe(II) occurred via reactive oxygen intermediates. This reoxidation could be avoided by either decreasing the oxygen concentration or by adding a Fe(II) stabilizing reagent, such as ferrozine. Further studies need to be done to confirm that these results apply at sub nanomolar concentrations, and the issue of Fe(II) reoxidation at lower Fe concentrations needs to be addressed.

Manganese (III) and manganese (IV) as chemiluminescence reagents : a review

Although potassium permanganate [Mn(VII)] has been used extensively as a chemiluminescence reagent for many decades, other manganese-based oxidants have only recently been explored for this purpose. There is strong evidence to suggest that, like permanganate, manganese(III) and manganese(IV) oxidants react with many molecules to produce an excited manganese(II) species that emits light. However, these reagents differ markedly in terms of selectivity, and possess characteristics that provide new avenues for detection, such as the immobilisation of solid manganese dioxide, the production of ‘soluble’ manganese(IV) nanoparticles, and the electrochemical generation of manganese(III). In this review we examine the emergence of these alternative manganese oxidants as chemiluminescence reagents.

Getting your life back on track after stroke : a phase II multi-centered, single-blind, randomized, controlled trial of the Stroke Self-Management Program vs. the Stanford Chronic Condition Self-Management Program or standard care in stroke survivors

Background Self-management is seen as a primary mechanism to support the optimization of care for people with chronic diseases such as symptomatic vascular disease. There are no established and evidence-based stroke-specific chronic disease self-management programs. Our aim is to evaluate whether a stroke-specific program is safe and feasible as part of a Phase II randomized-controlled clinical trial.
Methods Stroke survivors are recruited from a variety of sources including: hospital stroke services, local paper advertisements, Stroke South Australia newsletter (volunteer peer support organization), Divisions of General Practice, and community service providers across Adelaide, South Australia. Subjects are invited to participate in a multi-center, single-blind, randomized, controlled trial. Eligible participants are randomized to either;
• standard care,
• standard care plus a six week generic chronic condition self-management group education program, or,
• standard care plus an eight week stroke specific self-management education group program.
Interventions are conducted after discharge from hospital. Participants are assessed at baseline, immediate post intervention and six months.
Study Outcomes The primary outcome measures determine study feasibility and safety, measuring, recruitment, participation, compliance and adverse events.
Secondary outcomes include:
• positive and active engagement in life measured by the Health Education Impact Questionnaire,
• improvements in quality of life measured by the Assessment of Quality of Life instrument,
• improvements in mood measured by the Irritability, Depression and Anxiety Scale,
• health resource utilization measured by a participant held diary and safety.

Conclusion The results of this study will determine whether a definitive Phase III efficacy trial is justified.

Fish oil replacement in rainbow trout diets and total dietary PUFA content : II) Effects on fatty acid metabolism and in vivo fatty acid bioconversion

This study aimed to gain a better understanding of the metabolic fate of dietary fatty acids in rainbow trout, with a specific focus on the effect of varying total C18 PUFA level. Fish were fed a control fish oil based diet or one of five experimental fish oil deprived diets formulated with a constant 1/1 ratio of 18:3n-3/18:2n-6 and varying total C18 PUFA levels for a period of 7 weeks. The transcriptional changes of the Δ-6 desaturase and elongase enzymes in direct comparison to in vivo fatty acid bioconversion, estimated using the whole-body fatty acid balance method, were analysed. The main findings were that i) the efficiency of Δ-6 desaturase was negatively affected by C18 PUFA availability, but the total apparent in vivo enzyme activity was directly proportional to C18 PUFA substrate availability; ii) Δ-6 desaturase had a greater affinity towards n-3PUFA than n-6PUFA; iii) excessive C18 PUFA substrate availability could limit the availability of Δ-6 desaturase to act on C24 fatty acid; iv) the elimination of dietary n-3LC-PUFA (enzyme products) up-regulated the transcription rate of Δ-6 desaturase; but v) the total apparent in vivo enzyme activity was directly and positively affected by substrate availability, and not product presence/absence nor the extent of the enzyme transcription rate.

Phase II trial of continuous low-dose temozolomide for patients with recurrent malignant glioma

Background In this phase II trial, we investigated the efficacy of a metronomic temozolomide schedule in the treatment of recurrent malignant gliomas (MGs).

Methods Eligible patients received daily temozolomide (50 mg/m2) continuously until progression. The primary endpoint was progression-free survival rate at 6 months in the glioblastoma cohort (N = 37). In an exploratory analysis, 10 additional recurrent grade III MG patients were enrolled. Correlative studies included evaluation of 76 frequent mutations in glioblastoma (iPLEX assay, Sequenom) aiming at establishing the frequency of potentially “drugable” mutations in patients entering recurrent MG clinical trials.

Results Among glioblastoma patients, median age was 56 y; median Karnofsky Performance Score (KPS) was 80; 62% of patients had been treated for ≥2 recurrences, including 49% of patients having failed bevacizumab. Treatment was well tolerated; clinical benefit (complete response + partial response + stable disease) was seen in 10 (36%) patients. Progression-free survival rate at 6 months was 19% and median overall survival was 7 months. Patients with previous bevacizumab exposure survived significantly less than bevacizumab-naive patients (median overall survival: 4.3 mo vs 13 mo; hazard ratio = 3.2; P = .001), but those patients had lower KPS (P = .04) and higher number of recurrences (P < .0001). Mutations were found in 13 of the 38 MGs tested, including mutations of EGFR (N = 10), IDH1 (N = 5), and ERBB2 (N = 1).

Conclusions In spite of a heavily pretreated population, including nearly half of patients having failed bevacizumab, the primary endpoint was met, suggesting that this regimen deserves further investigation. Results in bevacizumab-naive patients seemed particularly favorable, while results in bevacizumab-failing patients highlight the need to develop further treatment strategies for advanced MG.

Bevacizumab for the treatment of high-grade glioma: an update after phase III trials.

Gliomas are highly vascular and rich in VEGF, which promotes angiogenesis. Bevacizumab is a monoclonal antibody against VEGF, inhibiting angiogenesis by preventing receptor activation. Early Phase II clinical trials using bevacizumab in both newly diagnosed and recurrent high-grade gliomas (HGG) showed promising results, but these have not been confirmed in recent Phase III trials. This review is an update including recently reported Phase II and III study results.

Dynamic regime marginal structural mean models for estimation of optimal dynamic treatment regimes, Part II: proofs of results

In this companion article to "Dynamic Regime Marginal Structural Mean Models for Estimation of Optimal Dynamic Treatment Regimes, Part I: Main Content" [Orellana, Rotnitzky and Robins (2010), IJB, Vol. 6, Iss. 2, Art. 7] we present (i) proofs of the claims in that paper, (ii) a proposal for the computation of a confidence set for the optimal index when this lies in a finite set, and (iii) an example to aid the interpretation of the positivity assumption.

Electrochemistry of tris(2,2′-bipyridyl) cobalt(II) in ionic liquids and aprotic molecular solvents on glassy carbon and platinum electrodes

The tris(2,2′-bipyridyl) complexes of cobalt(II) and (III) ([Co(bpy)3]^2+/3+) produce a redox couple of great interest in thermoelectrochemical cells and dye sensitized solar cells including both types of devices based on ionic liquid electrolytes. We present a systematic study of the electrochemistry of [Co(bpy)3]²⁺ [NTf2]^-2 in two ionic liquids (ILs) based on the 1-ethyl-3-methylimidazolium (C2mim) cation and two ILs based on the 1-butyl-1-methylpyrrolidinium cation (C4mpyr), as well as three aprotic molecular solvents. Platinum (Pt) and glassy carbon (GC) working electrodes were compared. In all solvents better electrochemical responses were observed on GC, which yielded higher currents in the cyclic voltammograms and lower rate constants for the redox reaction. The [Co(bpy)3]^1+/2+ couple is also readily observed, but this redox reaction is chemically irreversible, possibly because the [Co(bpy)3]¹⁺ complex dissociates. However, the [Co(bpy)3]^1+/2+ reaction is chemically reversible in all of the solvents studied, except 3-methoxypropionitrile, if excess of 2,2′-bipyridyl is added to the solution.