Copper® ion

Copper ions in the (I) and (II) oxidation state are biologically important. These ions appear to stabilize walls of certain blood vessels including the aorta and the sheath around the spinal cord. They are involved in the body s production of the color pigments of the skin, hair, and eyes, and in the in vivo synthesis of hemoglobin (232, 250). 

In certain copper-containing proteins the copper appears to serve principally in electron transport with no evidence of CU-O2 interaction, such as in cytochrome oxidase. Of importance, however, is that many copper proteins and enzymes participate in reactions in which the oxygen molecule is directly or indirectly involved. An example is hemocyanin, the oxygen carrier in the blood of certain sea animals such as snails, octopus, and Crustacea. Oxygenated hemocyanin is blue and the cephalopods (crabs and lobsters) are literally the blue bloods of the animal kingdom. Hemocyanins are giant molecules of MW 10 that occur free in solution. 

Both hemocyanin and tyrosinase, the enzyme that activates molecular oxygen for the oxidation of tyrosine, rely on direct covalent interaction between Cu(I) and O2, forming an observable dioxygen adduct. The mushroom Gyroporus cyanescens (Bluing Boletus), which turns blue instantly when bruised, also contains a copper protein or a blue protein, as it is called. 

Amino acid analyses of a variety of hemocyanins indicate that a large amount of histidine and methionine per copper pair is present as well as cysteine, although the number involved in disulfide bridges has not been determined. Intuitively, three types of donor atoms are likely to be involved in these protein complexes, namely, oxygen (carboxylate, phenolate, and water), nitrogen (amine, amide anion, and imidazole), and sulfur (thioether and thiolate). Furthermore, copper (II) can adopt square-planar, square-pyramidal, trigonal-bipyramidal, octahedral, and tetrahedral geometries. 

So far only a few biomodels of copper proteins have been made where the structure and ligand environments of the copper sites are based on the analysis of the electronic spectra. 

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Evans and co-workers investigated the effect of a number of -symmetric bis(oxazoline) ligands on the copper(II)-catalysed Diels-Alder reaction of an N-acyloxazolidinone with cyclopentadiene. Enantiomeric excesses of up to 99% have been reported (Scheme 3.4). Evans et al." suggested transition state assembly 3.7, with a square planar coordination environment around the central copper ion. In this scheme the dienophile should be coordinated predominantly in an cisoid fashion in... 

Interestingly, the rate constants for Diels-Alder reaction of the ternary complexes with 3.9 are remarkably similar. Only with 2,2 -bipyridine and 1,10-phenanthroline as ligands, a significant change in reactivity is observed. It might well be that the inability of these complexes to adopt a planar geometry hampers the interaction between the copper ion and the dienophile, resulting in a decrease of the rate of the catalysed Diels-Alder reaction. 

Fortunately, in the presence of excess copper(II)nitrate, the elimination reaction is an order of magnitude slower than the desired Diels-Alder reaction with cyclopentadiene, so that upon addition of an excess of cyclopentadiene and copper(II)nitrate, 4.51 is converted smoothly into copper complex 4.53. Removal of the copper ions by treatment with an aqueous EDTA solution afforded in 71% yield crude Diels-Alder adduct 4.54. Catalysis of the Diels-Alder reaction by nickel(II)nitrate is also... 

In this section the catalytic efficiency of Co(DS)2, Ni(DS)2, Cu(DS)2 andZn(DS)2 micelles as well as the effect of CTAB and C12E7 on the copper-ion catalysed Diels-Alder reaction between 5.1 and 5.2 is described... 

The enhanced binding predicts a catalytic potential for these solutions and prompted us to investigate the influence of the different types of micelles on the rate of the copper-ion catalysed reaction. Table 5.5 summarises the results, which are in perfect agreement with the conclusions drawn from the complexation studies. 

In all surfactant solutions 5.2 can be expected to prefer the nonpolar micellar environment over the aqueous phase. Consequently, those surfactant/dienophile combinations where the dienophile resides primarily in the aqueous phase show inhibition. This is the case for 5.If and S.lg in C12E7 solution and for S.lg in CTAB solution. On the other hand, when diene, dienophile and copper ion simultaneously bind to the micelle, as is the case for Cu(DS)2 solutions with all three dienophiles, efficient micellar catalysis is observed. An intermediate situation exists for 5.1c in CTAB or C12E7 solutions and particularly for 5.If in CTAB solution. Now the dienophile binds to the micelle and is slid elded from the copper ions that apparently prefer the aqueous phase. Tliis results in an overall retardation, despite the possible locally increased concentration of 5.2 in the micelle. 

The aromatic shifts that are induced by 5.1c, 5.If and S.lg on the H-NMR spectrum of SDS, CTAB and Zn(DS)2 have been determined. Zn(DS)2 is used as a model system for Cu(DS)2, which is paramagnetic. The cjkcs and counterion binding for Cu(DS)2 and Zn(DS)2 are similar and it has been demonstrated in Chapter 2 that Zn(II) ions are also capable of coordinating to 5.1, albeit somewhat less efficiently than copper ions. Figure 5.7 shows the results of the shift measurements. For comparison purposes also the data for chalcone (5.4) have been added. This compound has almost no tendency to coordinate to transition-metal ions in aqueous solutions. From Figure 5.7 a number of conclusions can be drawn. (1) The shifts induced by 5.1c on the NMR signals of SDS and CTAB... 

In contrast to the situation in the absence of catalytically active Lewis acids, micelles of Cu(DS)2 induce rate enhancements up to a factor 1.8710 compared to the uncatalysed reaction in acetonitrile. These enzyme-like accelerations result from a very efficient complexation of the dienophile to the catalytically active copper ions, both species being concentrated at the micellar surface. Moreover, the higher affinity of 5.2 for Cu(DS)2 compared to SDS and CTAB (Psj = 96 versus 61 and 68, respectively) will diminish the inhibitory effect due to spatial separation of 5.1 and 5.2 as observed for SDS and CTAB. 

The effects of these ligands on the second-order rate constants for the Cu (ligand) catalysed reaction of Ic with 2 are modest In contrast, the effects on IC2 are more pronounced. The aliphatic Oramino acids induce an approximately two-fold reduction of Iv relative to for the Cu" aquo ion. For the square planar coordinated copper ions this effect is expected on the basis of statistics. The bidentate ligands block half the sites on the copper centre. 

In contrast to SDS, CTAB and C12E7, CufDSjz micelles catalyse the Diels-Alder reaction between 1 and 2 with enzyme-like efficiency, leading to rate enhancements up to 1.8-10 compared to the reaction in acetonitrile. This results primarily from the essentially complete complexation off to the copper ions at the micellar surface. Comparison of the partition coefficients of 2 over the water phase and the micellar pseudophase, as derived from kinetic analysis using the pseudophase model, reveals a higher affinity of 2 for Cu(DS)2 than for SDS and CTAB. The inhibitory effect resulting from spatial separation of la-g and 2 is likely to be at least less pronoimced for Cu(DS)2 than for the other surfactants. 

Even ia 1960 a catalytic route was considered the answer to the pollution problem and the by-product sulfate, but nearly ten years elapsed before a process was developed that could be used commercially. Some of the eadier attempts iacluded hydrolysis of acrylonitrile on a sulfonic acid ion-exchange resia (69). Manganese dioxide showed some catalytic activity (70), and copper ions present ia two different valence states were described as catalyticaHy active (71), but copper metal by itself was not active. A variety of catalysts, such as Umshibara or I Jllmann copper and nickel, were used for the hydrolysis of aromatic nitriles, but aUphatic nitriles did not react usiag these catalysts (72). Beginning ia 1971 a series of patents were issued to The Dow Chemical Company (73) describiag the use of copper metal catalysis. Full-scale production was achieved the same year. A solution of acrylonitrile ia water was passed over a fixed bed of copper catalyst at 85°C, which produced a solution of acrylamide ia water with very high conversions and selectivities to acrylamide. 

Fig. 44. Schematic examples of facUitated transport of gases and metal ions. The gas-transport example shows the transport of oxygen across a membrane using hemoglobin (HEM) as the carrier agent. The ion-transport example shows the transport of copper ions across the membrane using a Uquid...

Dialkyl peroxydicarboaates are used primarily as free-radical iaitiators for viayl monomer po1ymeri2ations (18,208). Dialkyl peroxydicarboaate decompositioas are accelerated by certaia metals, coaceatrated sulfuric acid, and amines (44). Violent decompositions can occur with neat or highly concentrated peroxides. As with most peroxides, they Hberate iodine from acidified iodides. In the presence of copper ions and suitable substrates, dialkyl peroxydicarbonates have been used to synthesi2e alkyl carbonates (44) ... 

Apparently the alkoxy radical, R O , abstracts a hydrogen from the substrate, H, and the resulting radical, R" , is oxidized by Cu " (one-electron transfer) to form a carbonium ion that reacts with the carboxylate ion, RCO - The overall process is a chain reaction in which copper ion cycles between + 1 and +2 oxidation states. Suitable substrates include olefins, alcohols, mercaptans, ethers, dienes, sulfides, amines, amides, and various active methylene compounds (44). This reaction can also be used with tert-huty peroxycarbamates to introduce carbamoyloxy groups to these substrates (243). 

Pigment Blue 15 [147-14-8] 74160 copper phthalocyanine condensation of phthaUc anhydride with urea, in presence of copper ions, with or without added chlorophthahc anhy-dride subsequent conversion to alpha-phase and stabili2ation, if necessary... 

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... 

The potential of the reaction is given as = (cathodic — anodic reaction) = 0.337 — (—0.440) = +0.777 V. The positive value of the standard cell potential indicates that the reaction is spontaneous as written (see Electrochemical processing). In other words, at thermodynamic equihbrium the concentration of copper ion in the solution is very small. The standard cell potentials are, of course, only guides to be used in practice, as rarely are conditions sufftciendy controlled to be called standard. Other factors may alter the driving force of the reaction, eg, cementation using aluminum metal is usually quite anomalous. Aluminum tends to form a relatively inert oxide coating that can reduce actual cell potential. 

Textiles. Sorbitol sequesters iron and copper ions in strongly alkaline textile bleaching or scouring solutions (see Textiles). In compositions for conferring permanent wash-and-wear properties on cotton fabrics, sorbitol is a scavenger for unreacted formaldehyde (252) and a plasticizer in sod-resistant and sod-release finishes (253). 

If the cations in solution are condensable as a soHd, such as copper, they can plate out on the cathode of the cell. As the same time, perhaps some hydrogen is also produced at the cathode. The SO can react with a copper anode material by taking it into solution to replace the lost copper ions. Thus the anode is a consumable electrode in the process. 

In addition to bonding with the metal surface, triazoles bond with copper ions in solution. Thus dissolved copper represents a "demand" for triazole, which must be satisfied before surface filming can occur. Although the surface demand for triazole filming is generally negligible, copper corrosion products can consume a considerable amount of treatment chemical. Excessive chlorination will deactivate the triazoles and significantly increase copper corrosion rates. Due to all of these factors, treatment with triazoles is a complex process. 

Aetivators. These are used to make a mineral surface amenable to collector coating. Copper ion is used, for example, to activate sphalerite (ZnS), rendering the sphalerite surface capable of absorbing a xanthate or dithiophosphate collector. Sodium sulfide is used to coat oxidized copper and lead minerals so that they can be floated by a sulfide mineral collector. 

Voluminous corrosion products are usually absent, as most copper amine complexes are quite soluble. Adjacent to corroded areas, one often finds small amounts of corrosion products and deposits colored a vivid blue-green by compounds containing liberated copper ion. 

Aluminum components are sensitive to ions of heavy metals, especially copper. To avoid localized galvanic corrosion of the aluminum by metallic copper reduced from copper ions, care must be exercised to prevent heavy metal ions from entering aluminum components. Note the recommendations under Elimination. ... 

An interesting effect is sometimes observed when cupronickels are galvanically coupled to less noble materials. The corrosion rate of the active metal is increased and the corrosion rate of the cupronickel is diminished, as expected. The diminished corrosion rate of the cupronickel can, however, diminish its fouling resistance since reduced production of copper ions lowers toxicity to copper-ion-sensitive organisms. 

Deionization of copper ions is natural and extremely fast... 

Figure 3 Positive-ion mass spectrum acquired from defective sampie. intense copper ion signals are observed iM/Z = 63 and 65).

Figure 4 Positive-ion mass spectrum acquired from the contact region of a control sample. Copper ion signals are absent.

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