Reduced state

HSCH2CH(0H)CH(0H)CH2SH. a useful water soluble reagent for preserving thiols in the reduced state, and for reducing disulphides quantitatively to dithiols. 

Note that the equation for metal-metal ion systems is a special case of this general equation since the reduced state is the metal itself and the concentration of a solid is a constant and omitted from the equation.)... 

The tap T2 is now closed. The furnace is switched off and the carbon dioxide generator left on until the combustion tube is cold this ensures that the reduced copper spiral, by cooling in carbon dioxide, is main tained in the reduced state. (Despite this precaution it does become spent and should be replaced from time to time. A spent copper spiral leads to high results, but before this takes place there is usually suffici-... 

Among the various classes of hydrocarbons alkanes contain carbon m its most reduced state and alkynes contain carbon m its most oxidized state... 

You will recall from Chapter 6 that the Nernst equation relates the electrochemical potential to the concentrations of reactants and products participating in a redox reaction. Consider, for example, a titration in which the analyte in a reduced state, Ared) is titrated with a titrant in an oxidized state, Tox- The titration reaction is... 

Acidic Properties. As a typical acid, it reacts readily with alkaUes, basic oxides, and carbonates to form salts. The largest iadustrial appHcation of nitric acid is the reaction with ammonia to produce ammonium nitrate. However, because of its oxidising nature, nitric acid does not always behave as a typical acid. Bases having metallic radicals ia a reduced state (eg, ferrous and staimous hydroxide becoming ferric and stannic salts) are oxidized by nitric acid. Except for magnesium and manganese ia very dilute acid, nitric acid does not Hberate hydrogen upon reaction with metals. 

Traditionally, these dyes are appHed from a dyebath containing sodium sulfide. However, development in dyeing techniques and manufacture has led to the use of sodium sulfhydrate, sodium polysulfide, sodium dithionite, thiourea dioxide, and glucose as reducing agents. In the reduced state, the dyes have affinity for cellulose (qv) and are subsequendy exhausted on the substrate with common salt or sodium sulfate and fixed by oxidation. 

Metal Deactivators. The abiUty of metal ions to catalyse oxidation can be inhibited by metal deactivators (19). These additives chelate metal ions and increase the potential difference between the oxidised and reduced states of the metal ions. This decreases the abiUty of the metal to produce radicals from hydroperoxides by oxidation and reduction (eqs. 15 and 16). Complexation of the metal by the metal deactivator also blocks its abiUty to associate with a hydroperoxide, a requirement for catalysis (20). 

Vat dyes are water-soluble ki the reduced state but extremely kisoluble ki the oxidi2ed anthraqukione state (see Dyes, anthraquinone). As an example. Figure 2 shows the soluble and oxidi2ed states for Vat Yellow 3, used as a yellow colorant ki several lenses. The water-soluble form of the dye is allowed to diffuse kito the polymer matrix for a specified amount of time. The dye is then treated with a mild oxidi2kig agent and the kisoluble form is precipitated. The tints are extremely colorfast and stable for the life of the lens however, the dyes are unstable ki the soluble form and quite expensive. 

Dicarbocyanine and trie arbo cyanine laser dyes such as stmcture (1) (n = 2 and n = 3, X = oxygen) and stmcture (34) (n = 3) are photoexcited in ethanol solution to produce relatively long-Hved photoisomers (lO " -10 s), and the absorption spectra are shifted to longer wavelength by several tens of nanometers (41,42). In polar media like ethanol, the excited state relaxation times for trie arbo cyanine (34) (n = 3) are independent of the anion, but in less polar solvent (dichloroethane) significant dependence on the anion occurs (43). The carbocyanine from stmcture (34) (n = 1) exists as a tight ion pair with borate anions, represented RB(CgH5 )g, in benzene solution photoexcitation of this dye—anion pair yields a new, transient species, presumably due to intra-ion pair electron transfer from the borate to yield the neutral dye radical (ie, the reduced state of the dye) (44). 

Metal ions in their reduced state also undergo reactions with BrCl. Examples include iron and manganese. 

The substrates of catabolism—proteins, carbohydrates, and lipids—are good sources of chemical energy because the carbon atoms in these molecules are in a relatively reduced state (Figure 18.9). In the oxidative reactions of catabolism, reducing equivalents are released from these substrates, often in the form of hydride ions (a proton coupled with two electrons, H ). These hydride ions are transferred in enzymatic dehydrogenase reactions from the substrates... 

The second step involves the transfer of electrons from the reduced [FMNHg] to a series of Fe-S proteins, including both 2Fe-2S and 4Fe-4S clusters (see Figures 20.8 and 20.16). The unique redox properties of the flavin group of FMN are probably important here. NADH is a two-electron donor, whereas the Fe-S proteins are one-electron transfer agents. The flavin of FMN has three redox states—the oxidized, semiquinone, and reduced states. It can act as either a one-electron or a two-electron transfer agent and may serve as a critical link between NADH and the Fe-S proteins. 

Cytochrome c, like UQ is a mobile electron carrier. It associates loosely with the inner mitochondrial membrane (in the intermembrane space on the cytosolic side of the inner membrane) to acquire electrons from the Fe-S-cyt C aggregate of Complex 111, and then it migrates along the membrane surface in the reduced state, carrying electrons to cytochrome c oxidase, the fourth complex of the electron transport chain. 

Some data have been obtained on the activity of the catalyst in a reduced state [for nickel (141,143,144), palladium (144°), and molybdenum (145, 145a). In the case of nickel catalysts the formation of nickel in the zero oxidation state takes place during the reduction of the surface organometallic compound by H2. The infrared spectrum shows the total restoration of the concentration of Si—OH groups (139), so the reduction proceeds according to the scheme ... 

Saturday, December 19, 1942. Today Thompson tested the use of bismuth phosphate as a carrier for 94 in its reduced state with rather encouraging results. Upon precipitating relatively high concentrations of bismuth (15-25 mg per 10 cc) as bismuth phosphate from 20% UNH solution, he finds the 94 to be carried to the extent of more than 85%. The bismuth phosphate precipitates are slow in forming and require digestion at temperatures of the order of 75°C. 

The rate of water transport through polyaniline has been measured by mass spectrometry.198 Consistent with the gravimetric results cited above, the permeability of the oxidized state was found to be much higher than that of the reduced state. 

Polynuclear transition metal cyanides such as the well-known Prussian blue and its analogues with osmium and ruthenium have been intensely studied Prussian blue films on electrodes are formed as microcrystalline materials by the electrochemical reduction of FeFe(CN)g in aqueous solutionThey show two reversible redox reactions, and due to the intense color of the single oxidation states, they appear to be candidates for electrochromic displays Ion exchange properties in the reduced state are limited to certain ions having similar ionic radii. Thus, the reversible... 

In its reduced state, the paramagnetic Rieske cluster shows a temperature-dependent MOD spectrum composed of numerous positive and negative C-terms that originate from the 8 = 1 ground state. The MOD spectra lack the Fe" 8 charge transfer bands that are observed as intense negative bands between 300 and 350 nm and a posi-... 

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