Cellulose, electrochemical oxidation

F. X. Redl, O. Kothe, K. Roekl, W. Bauer, and J. Daub, Azulene-appended cellulose Synthesis, optieal and ehiroptical properties, film formation by electrochemical oxidation, Macromol. Chem. Phys., 201 (2000) 2091-2100. 

The second approach for improving the processabihty of ICPs is to prepare their colloidal dispersions in water or an appropriate solvent The colloid dispersions of ICPs can be obtained by chemical or electrochemical oxidation of the monomer in the presence of a steric stabihzer [29-31].The key parameter for such synthesis is the choice of an appropriate steric stabihzer which adsorbs or grafts onto the polymer coUoidal particles to prevent their aggregation or precipitation. Several polymers such as polyfethylene oxide) [32], poly(vinyl pyrroHdone) [33,34], poly(vinyl alcohol) [35], ethyl hydroxy cellulose [36], poly(vinyl alcohol-co-acetate) [37], poly(vinyl methyl ether) [38,39] and block copolymer stabihzer [40] have been used as steric stabihzers to produce PPy coUoidal dispersions. Surfactants are also employed for the synthesis of ICP coUoidal dispersions [41,42]. Very recently, stable PPy dispersions were prepared by Lu et al. by polymerizing pyrrole in an aqueous medium containing different anionic salts such as sodium benzoate, potassium hydrogen phthalate, and sodium succinate [43]. These authors also reported that the conductivity of PPy dispersions was enhanced when sodium benzoate was used as dopant. Chemical oxidahve polymerization in the presence of PSS in aqueous medium produces coUoidal dispersions and improves processability [44]. CoUoidal dispersions... 

Heterocyclophane 177e was also obtained on a platinum cylindrical electrode by the preparative electrochemical oxidation of podand 158e in a diaphragm (cellulose) glass electrolyzer. The electrosynthesis was carried out for 4 h. The mass spectrometric investigations of the mixture after the electrolysis showed the existence of two macrocyclic products 152e (m/z = 830), and the macrocyclic dimer (m/z = 1660). The preparative yield was 40 % (Mamedov et al. 2007). There was no starting compound in the solution. 

Most commonly used separator materials for alkaline Zn/Mn02 batteries are nonwoven polymers, such as cellulose, vinyl polymers, polyolefin, and others. The separator materials must be chemically stable in concentrated KOH solutions and electrochemically stable under both oxidizing and reducing conditions in the cell. In addition to its good electronic insulation, physical strength, and porous structure, good wettability to concentrated KOH solutions is especially crucial to provide a good ionic pathway for the battery operation. 

Chiral disubstituted PEDOTs have recently been prepared for the first time via transetherification of 3,4-dimethoxythiophene monomers with chiral glycols followed by potentiodynamic oxidation.174 An alternative approach to optically active PEDOTs has also been recently described, which involves the electrochemical polymerization of the EDOT monomer in aqueous hydroxypropyl cellulose (HPC) as a polymer lyotropic liquid crystal to give a chiral PEDOT/HPC hybrid.175 The PEDOT prepared in this chiral nematic liquid crystal exhibited optically active electrochromism in that it could be electrochemically switched between a dark blue reduced state and a sky blue oxidized form that exhibited a different CD spectrum. 

Even compounds with a complex structure such as cellulose can be oxidized quantitatively to CO2 using platinized-platinum electrocatalysts (100). This is of interest because of the difficulty of chemical or biochemical oxidation of cellulose. A cellulose-air fuel cell could yield about 1 mw cm of power. The disposal of body wastes could be accelerated electrochemically. 

Figure lA shows the normalized electrochemical charge, Q gx> function of hydrolysis time for a 170 10 nm film of cellulose acetate at GC. The ordinate, Q ox Figure lA equals K CQg /n), where K equals the ratio of the concentrations of -NADH or Fe(CN)g to that of HQ, and n Is the number of electrons generated by the oxidation reaction. The n value for HQ and -NADH equals... 

The analytical application of particle-dispersed-modified electrodes to the selective detection of a single analyte is limited because of broad catalytic activities thus their use as electrochemical detectors following chromatographic separation of carbohydrates is often suggested. Similar nonspecific catalytic PMEs consisting of electrocatalytic RUO2 particles and Ru(OH2)6 in Nafion have been shown to catalyze the oxidation of catechol and of alcohols, respectively these could presumably be used in place of the carbon paste Ru02-modified electrode developed for postseparation detection of carbohydrates and alcohols. Other electrocatalytic particle electrodes were prepared from lead dioxide in polypyrrole and CoPc entrapped behind a permselective cellulose acetate film. ... 

Nitrite Nitrite is an important indicator of fecal pollution in natural waters as well as a potential precursor of carcinogenic species. A rush of flow and sequential injection spectrophotometric method based on Griess-type reactions has been proposed, also coupled to online sorbent enrichment schemes. The catalytic effect of nitrite on the oxidation of various organic species constitutes the basis of fairly sensitive spectrophotometric methods. Fluorometric methods based on the formation of aromatic azoic acid salts, quenching of Rhodamine 6G fluorescence, and direct reaction with substituted tetramine or naphthalene species have been also reported. Indirect CL methods usually involve conversion into nitric oxide and gas-phase detection as mentioned in the foregoing section. The redox reaction between nitrite and iodide in acidic media is the fundamental of a plethora of flow injection methodologies with spectrophotometric, CL, or biamperometric detection. New electrochemical sensors with chemically modified carbon paste electrodes containing ruthenium sites, or platinum electrodes with cellulose or naphthalene films, have recently attracted special attention for amperometric detection. 

Active enzymes were encapsulated into a sol-gel matrix for the first time in 1990 719 About 60 different types of hybrid bioceramic materials with inotganic matrices made from silicon, titanium, and zirconium oxides Ti02-cellulose composites etc. were described. Recentiy, bioceramic sensors, solid electrolytes, electrochemical biosensors, etc. have been surveyed in a review. The moderate temperatures and mild hydrolytic and polymerization conditions in sol-gel reactions of alkoxides make it possible to trap proteins during matrix formation. This prevent proteins denaturation. The high stability of the trapped biomolecules, the inertness, the large specific surface, the porosity, and the optical transparency of the matrix facilitate use of sol-gel immobilization. The principal approaches ate considered below. 

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