Copper ion complexes

Protection of the enzyme by a copper ion complexing agent (EDTA) to avoid inhibition by traces of copper ions from the copper catalyst. 

Figure 7.48 Two cytochrome c oxidase Cua center model compounds (A) delocalized core with two i-l,3-(KN KO)-ureate bridges as reported in reference 165-and (B) a dithiolate-bridged mixed-valence binuclear copper ion complex as re in reference 166.

Increasing the pH of copper alginate beads with sodium hydroxide will probably not cause the beads to dissolve. Adding beads to concentrated ammonia solution, however, will slowly dissolve the beads because the copper ions complex more strongly with NH3 (forming the deep blue Cu(NH3)42+) than they do with carboxy-late ions. 

It has been shown that organofunctionalized silica surfaces further modified with in situ synthesized copper complexes can be used to produce new stationary phases for HPLC [4]. The immobilized copper complexes provide new sites in the stationary phase that can interact strongly with basic organic compounds. A test mixture of compounds such as benzene, toluene, naphthalene, anthracene, pyrene, and nitrobenzene shows that the presence of copper ion complexes on the modified surface strongly affects the retention factor (fe) of the stationary phases. 

As already introduced in Section 2.4, angular dependent NEXAFS spectroscopy is a powerful tool in the study of self assembled systems, and was successfully applied to the investigation of self assembled monolayers and multilayers of molecular-based NLO materials. Among others, Bubeck and co-workers [70] investigated the interaction of Cu " with C, N and O moieties in nanocomposites containing copper ions complexed in poly(amidoamine-organosilicon), PAMAMOS (dendrimer molecular structure is shown in Fig. 4.19). 

Peptides and proteins can effectively complex copper ions, although the extent depends on the structure of the peptide [104]. The copper ion complexation in homopolypeptides is even strong enough to protect the backbcme from racemi-zation in the alkaline deprotection of, e.g., PBLG [105]. Therefore, the solvent and the ligand for the ATRP catalyst system have to be chosen accordingly to suppress complexation by the peptide chains [79]. 

H. E. Hajji, E. Nkhili, V. Tomao, and O. Dangles, Interactions of quercetin with iron and copper ions complexation and autoxidation, Free Radical Research, vol. 40, no. 3, pp. 303-320, 2006. 

Kim et al. published an assay based on UV-Vis spectrometry [149]. As shown in Scheme 29.17a the a-amino acid produced during the reaction was stained with a solution containing CuSO /MeOH, forming a blue-colored copper ion complex, which can be quantified at 595 nm, whereas other substrates like amines, p-amino acids, a-keto acids, or ketones showed no color after adding the CuSO /MeOH solution. A major drawback of this method is the color complex, formed by a-amino acids in a phosphate buffer with cupric sulfate also absorbing at 595 nm. Hence, sufficient dialysis of the enzyme or the crude cell extracts has to be conducted. 

Huang, Z., Cheng, S., Zeng, X. Catalytic hydrolysis of p-nitrophenyl acetate by copper ion complexes of diamine-based ligands in CTAB micellar solution. J. Dispersion Sci. Technol. 2003, 24(2), 213-218. 

The anhydrous chloride is prepared by standard methods. It is readily soluble in water to give a blue-green solution from which the blue hydrated salt CuClj. 2H2O can be crystallised here, two water molecules replace two of the planar chlorine ligands in the structure given above. Addition of dilute hydrochloric acid to copper(II) hydroxide or carbonate also gives a blue-green solution of the chloride CuClj but addition of concentrated hydrochloric acid (or any source of chloride ion) produces a yellow solution due to formation of chloro-copper(ll) complexes (see below). 

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... 

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 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. 

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. 

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. 

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. 

Metal ion complexes. These classic CSPs were developed independently by Davankov and Bernauer in the late 1960s. In a typical implementation, copper (II) is complexed with L-proline moieties bound to the surface of a porous polymer support such as a Merrifield resin [28-30]. They only separate well a limited number of racemates such as amino acids, amino alcohols, and hydroxy acids. 

K has the value of about 1 x 10 at 298 K, and in solutions of copper ions in equilibrium with metallic copper, cupric ions therefore greatly predominate (except in very dilute solutions) over cuprous ions. Cupric ions are therefore normally stable and become unstable only when the cuprous ion concentration is very low. A very low concentration of cuprous ions may be produced, in the presence of a suitable anion, by the formation of either an insoluble cuprous salt or a very stable complex cuprous ion. Cuprous salts can therefore exist in contact with water only if they are very sparingly soluble (e.g. cuprous chloride) or are combined in a complex, e.g. [Cu(CN)2) , Cu(NH3)2l. Cuprous sulphate can be prepared in non-aqueous conditions, but because it is not sparingly soluble in water it is immediately decomposed by water to copper and cupric sulphate. 

Fast sulphon black F ( C.I.26990). This dyestuff is the sodium salt of 1-hydroxy-8-( 2-hydroxynaphthylazo) -2- (sulphonaphthylazo) -3,6-disulph onic acid. The colour reaction seems virtually specific for copper ions. In ammoniacal solution it forms complexes with only copper and nickel the presence of ammonia or pyridine is required for colour formation. In the direct titration of copper in ammoniacal solution the colour change at the end point is from magenta or [depending upon the concentration of copper(II) ions] pale blue to bright green. The indicator action with nickel is poor. Metal ions, such as those of Cd, Pb, Ni, Zn, Ca, and Ba, may be titrated using this indicator by the prior addition of a reasonable excess of standard copper(II) solution. 

It should be noted that this method is only applicable to solutions containing up to 25 mg copper ions in 100 mL of water if the concentration of Cu2+ ions is too high, the intense blue colour of the copper(II) ammine complex masks the colour change at the end point. The indicator solution must be freshly prepared. 

Discussion. The titration of a copper ion solution with EDTA may be carried out photometrically at a wavelength of 745 nm. At this wavelength the copper-EDTA complex has a considerably greater molar absorption coefficient than the copper solution alone. The pH of the solution should be about 2.4. 

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