Cupric detection

The potentiometric micro detection of all aminophenol isomers can be done by titration in two-phase chloroform-water medium (100), or by reaction with iodates or periodates, and the back-titration of excess unreacted compound using a silver amalgam and SCE electrode combination (101). Microamounts of 2-aminophenol can be detected by potentiometric titration with cupric ions using a copper-ion-selective electrode the 3- and... 

In a similar procedure, the atomizer test, which depends on the behavior of an advancing rather than a receding contact angle, a fine mist of water is apphed to the metal surface and the spreading of water is observed. On a clean surface, water spreads to a uniform film. With oleic acid as the test soil, the atomizer test can detect the presence of 10 mg of soil per cm, less than a monomolecular layer (115). For steel that is to be electroplated, the copper dip test is often employed. Steel is dipped into a cupric salt solution and the eveimess of the resulting metallic copper deposit is noted. 

What about the state of equilibrium for the reaction represented by equation (11)1 Let us place a strip of metallic copper in a zinc sulfate solution. No visible reaction occurs and attempts to detect the presence of cupric ion by adding H2S to produce the black color of cupric sulfide, CuS, fail. Cupric sulfide has such low solubility that this is an extremely sensitive test, yet the amount of Cu+2 formed cannot be detected. Apparently the state of equilibrium for the reaction (11) greatly favors the products over the reactants. 

Some observations are important for improvement of the yield and for the elucidation of the mechanism of the Meerwein reaction. Catalysts are necessary for the process. Cupric chloride is used in almost all cases. The best arylation yields are obtained with low CuCl2 concentrations (Dickerman et al., 1969). One effect of CuCl2 was detected by Meerwein et al. (1939) in their work in water-acetone systems. They found that in solutions of arenediazonium chloride and sodium acetate in aqueous acetone, but in the absence of an alkene, the amount of chloroacetone formed was only one-third of that obtained in the presence of CuCl2. They concluded that chloroacetone is formed according to Scheme 10-50. The formation of chloroacetone with CuCl2 in the absence of a diazonium salt (Scheme 10-51) was investigated by Kochi (1955 a, 1955 b). Some Cu11 ion is reduced by acetone to Cu1 ion, which provides the electron for the transfer to the diazonium ion (see below). 

A modification of the RDC design, based on the ring-disk arrangement of the RDE [36], incorporated an arc electrode [37,38] deposited on the surface of the membrane around the untreated area. This facilitated the electrochemical detection of species reacting at the interface at short times following the reaction. This method was used to study the solvent extraction of cupric ions, which were detected by reduction to copper metal at the arc electrode. The resulting current flow was related to the interfacial flux at the membrane. 

There are no approved pharmacologic treatments for atrophic AMD. The Age-Related Eye Disease Study showed that a supplement containing ascorbic acid 500 mg, vitamin E 400 IU, beta carotene 15 mg, zinc oxide 80 mg, and cupric oxide 2 mg reduced the rate of clinical progression of all types of AMD by 28% in patients with at least intermediate macular degeneration. No benefit was seen in patients with earlier stages of age-related maculopathy however, the duration of the study may have been insufficient to detect this benefit.25... 

The hemispherical electrode may be coupled with a ring [20] to form a rotating ring-hemisphere electrode (RRHSE) as shown as Fig. 9(d). The ability of this combination to detect intermediate reaction products is demonstrated in Fig. 10, where a series of cathodic sweep curves for the reduction of Cu2 + in acidic cupric chloride solution are... 

Most biochemically relevant high-spin systems have such short 7j-relaxation times that their EPR is broadened beyond detection at ambient temperatures. An exception is the class of S = 5/2 Mn" systems with D hx. Also, S = 7/2 Gd"1-based MRI shift reagents exhibit readily detectable room-temperature EPR spectra. Otherwise, aqueous-solution transition ion bioEPR is limited to complexes of S = 1/2 metals, in particular Cu", and to a lesser extent VIV02+, NiIn, Ni1, Mov, and Wv. Cupric is the stable oxidation state of biological copper under aerobic conditions, however, the other metals are stable as Vv, Ni", MoVI, and WVI, and, therefore, the other oxidation states associated with S = 1/2 paramagnetism may exhibit oxidative or reductive reactivity and may thus require specific experimental precautions such as strict anaerobicity over the course of the EPR experiment. 

K.N. Thomsen and R.P. Baldwin, Amperometric detection of non-electroactive cations in flow systems at a cupric hexacyanoferrate electrode. Anal. Chem. 61, 2594—2598 (1989). 

Nickel or cupric hexacyanoferrate film electrodes have been also used for amperometric detection of intercalating ions in a flow-injection system (K+ and NH4+ in urine and K+ in blood samples)... 

No activation of hydrogen by the cupric species can be detected. It is not possible, however, to rule out activities of the order of those exhibited by cupric salts in aqueous or heptanoic acid solution, since these would probably be masked by the very high activity of the cuprous species in this system. 

The results show that a number of ruthenium carbonyl complexes are effective for the catalytic carbonylation of secondary cyclic amines at mild conditions. Exclusive formation of N-formylamines occurs, and no isocyanates or coupling products such as ureas or oxamides have been detected. Noncyclic secondary and primary amines and pyridine (a tertiary amine) are not effectively carbonylated. There appears to be a general increase in the reactivity of the amines with increasing basicity (20) pyrrolidine (pKa at 25°C = 11.27 > piperidine (11.12) > hexa-methyleneimine (11.07) > morpholine (8.39). Brackman (13) has stressed the importance of high basicity and the stereochemistry of the amines showing high reactivity in copper-catalyzed systems. The latter factor manifests itself in the reluctance of the amines to occupy more than two coordination sites on the cupric ion. In some of the hydridocar-bonyl systems, low activity must also result in part from the low catalyst solubility (Table I). 

In sum, the cupric ion transfers an electron from the unsaturated substrate to the diazo-nium cation, and the newly formed diazonium radical quickly loses nitrogen. The aryl radical formed attacks the ethylenic bond within the active complexes that originated from the [aryldiazonium tetrachlorocuprate(II)-olefin] or [initial arydiazonium salt-catalyst-olefin] associate and yields the >C(Ar)—C < radical. The latter was detected by ESR spectroscopy. The formation of both the cation radical [>C=C<]+ and the radical >C(Ar)—C < as intermediates indicates that the reaction involves two catalytic cycles. In the other case, the radical >C(Ar)—C < will not be formed, being consumed in the following reaction ... 

Cupric sulfate-quinine-pyridine A solution that is 0.4% in cupric sulfate, 0.04% in quinine hydrochloride, and 4% in pyridine in water is sprayed on the plate followed by a 0.5% aqueous potassium permanganate solution. A variety of colors (white, yellow, violet) are detected on the chromatogram. 

Funazo et al. [812] have described a method for the determination of cyanide in water in which the cyanide ion is converted into benzonitrile by reaction with aniline, sodium nitrite and cupric sulphate. The benzonitrile is extracted into chloroform and determined by gas chromatography with a flame ionisation detector. The detection limit for potassium cyanide is 3 mg L 1. Lead, zinc and sulphide ion interfere at lOOmg L 1 but not at lOmgL-1. 

Powdered black copper oxide when stirred into water gives a black suspension and does not visibly dissolve. If the suspension is allowed to stand the black powder settles to the bottom and the clear liquid above contains so few ions of Cu++ and OH that they cannot be detected by the reagents commonly used for detecting these ions, NH4OH, Na2S. Yet we are confronted with the fact that, when acid is added to the suspension of copper oxide, the black powder dissolves completely and we obtain a clear blue solution of the cupric salt. The initial and final substances in this reaction are given in the equation... 

As has been mentioned in 1, smooth surfaces of copper, including those deposited electrolytically, reduced copper mirrors, and polished surfaces were quite inactive (a, i) a minute trace of activity only was occasionally detected in commercial copper gauze, but copper prepared by thermal decomposition of either cupric or cuprous oxides, or copper salts of mono- and dibasic fatty acids, by condensation on china-clay rods2 from the vapour (in nitrogen, to prevent oxidation), or by stirring up the atoms of copper into open formation by heating in ammonia at 820°, was active (t). 

A series of hemocyanin and tyrosinase active site derivatives (Fig. 23) can be prepared61"66), allowing systematic variation of the binuclear copper active site and chemical perturbation for spectral studies. In the simplest derivative, met-apo, one copper has been removed and the remaining copper oxidized to the spectroscopically accessible Cu(II). Next in complexity is a mixed-valent binuclear copper site. The Cu(II), in this half-met derivative, exhibits open-shell d9 spectroscopic features and the Cu(I), though spectroscopically inaccessible, can still be studied by comparison to the met-apo derivative. Two derivatives have formally binuclear cupric sites met, which is EPR-non-detect-able, and dimer, which exhibits an intense broad EPR signal. Spectroscopic study of these derivatives has led to the present picture of the coupled binuclear copper protein active site shown at the bottom of Fig. 23. 

Interest in the subject was revived in 1907 by Ramsay s 7 announcement of the development of spectroscopic quantities of lithium in solutions of cupric sulphate or nitrate exposed to the radium emanation. In control experiments made without the emanation no lithium was detected. ilme. Curie and Mile. Gleditsch8 repeated Ramsay s experiments, employing vessels of platinum instead of glass, but failed to detect the development of even a trace of lithium. They attribute Ramsay s results to solution of lithium present in the glass of his apparatus. Mile. Gleditsch9 detected the presence of lithium in a sample of pitchblende from Joachimsthal, as well as in other radioactive minerals, but failed to find any simple relationship between the proportion of lithium and copper present in the minerals examined. The results10 are summarized in the table ... 

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